U.S. patent application number 15/307637 was filed with the patent office on 2017-03-02 for liquid crystal display device.
This patent application is currently assigned to DIC CORPORATION (TOKYO). The applicant listed for this patent is DIC Corporation (Tokyo). Invention is credited to Yoshinori IWASHITA, Jouji KAWAMURA, Yoshiyuki ONO, Hiroyuki TAKEDA.
Application Number | 20170058160 15/307637 |
Document ID | / |
Family ID | 55162620 |
Filed Date | 2017-03-02 |
United States Patent
Application |
20170058160 |
Kind Code |
A1 |
ONO; Yoshiyuki ; et
al. |
March 2, 2017 |
LIQUID CRYSTAL DISPLAY DEVICE
Abstract
The present invention relates to a liquid crystal display device
including a particular liquid crystal composition and a cured
product of a particular curable resin composition serving as a
sealant. The present invention provides a liquid crystal display
device that does not suffer from a decrease in the voltage holding
ratio (VHR) or increase in the ion density (ID) of the liquid
crystal layer or the problem of display defects such as white
spots, alignment unevenness, and image-sticking. Since the liquid
crystal display device according to the present invention does not
suffer from a decrease in the voltage holding ratio (VHR) of the
liquid crystal layer or display defects such as alignment
unevenness and image-sticking, the liquid crystal display device is
particularly useful as an active-matrix-driven liquid crystal
display device such as a VA, PSVA, IPS, or FFS liquid crystal
display device and can be used as a liquid crystal display device
for products such as liquid crystal display televisions, monitors,
cell phones, and smartphones.
Inventors: |
ONO; Yoshiyuki;
(Kita-adachi-gun, JP) ; KAWAMURA; Jouji;
(Kita-adachi-gun, JP) ; IWASHITA; Yoshinori;
(Kita-adachi-gun, JP) ; TAKEDA; Hiroyuki;
(Sakura-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DIC Corporation (Tokyo) |
Tokyo |
|
JP |
|
|
Assignee: |
DIC CORPORATION (TOKYO)
Tokyo
JP
|
Family ID: |
55162620 |
Appl. No.: |
15/307637 |
Filed: |
July 23, 2014 |
PCT Filed: |
July 23, 2014 |
PCT NO: |
PCT/JP2014/069411 |
371 Date: |
October 28, 2016 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09J 133/068 20130101;
C09K 2019/521 20130101; G02F 1/0045 20130101; C09K 2019/3004
20130101; C09K 19/322 20130101; C09K 19/3003 20130101; C08F
220/1804 20200201; C09J 135/02 20130101; C09J 133/068 20130101;
C09K 2019/3025 20130101; C09K 2019/3013 20130101; C08F 222/1067
20200201; C09K 2019/3027 20130101; C08G 59/1477 20130101; C09K
19/42 20130101; G02F 1/1339 20130101; C09K 2019/123 20130101; C08G
59/1466 20130101; C09K 2019/3016 20130101; C09J 133/066 20130101;
C09J 133/10 20130101; C09K 19/3066 20130101; C09J 133/066 20130101;
C08F 220/20 20130101; C08F 220/20 20130101; C08F 212/08 20130101;
C08F 220/325 20200201; C08F 220/14 20130101; C08L 63/04 20130101;
C08F 220/1804 20200201; C08L 63/04 20130101; C09J 163/10 20130101;
C08F 220/1804 20200201; C09K 2019/122 20130101; C08F 220/18
20130101; G02F 1/133365 20130101; C08F 222/1065 20200201; C09K
2019/3009 20130101; C09K 19/542 20130101; C09K 2019/301 20130101;
C08L 63/04 20130101; C08F 220/14 20130101; C08F 212/08 20130101;
C08F 220/325 20200201 |
International
Class: |
C09J 163/10 20060101
C09J163/10; C08G 59/17 20060101 C08G059/17; C08G 59/14 20060101
C08G059/14; G02F 1/1333 20060101 G02F001/1333; C09J 135/02 20060101
C09J135/02; C09K 19/30 20060101 C09K019/30; C09K 19/32 20060101
C09K019/32; G02F 1/1339 20060101 G02F001/1339; C08F 220/18 20060101
C08F220/18; C09J 133/10 20060101 C09J133/10 |
Claims
1. A liquid crystal display device comprising a first substrate, a
second substrate, a liquid crystal layer comprising a liquid
crystal composition between the first and second substrates, and a
cured product of a thermally curable resin composition joining
together the first and second substrates, the liquid crystal
composition comprising: 10% to 50% of a compound represented by
general formula (I): ##STR00022## (wherein R.sup.1 and R.sup.2 are
each independently an alkyl group of 1 to 8 carbon atoms, an
alkenyl group of 2 to 8 carbon atoms, an alkoxy group of 1 to 8
carbon atoms, or an alkenyloxy group of 2 to 8 carbon atoms; and A
is 1,4-phenylene or trans-1,4-cyclohexylene); and 35% to 80% by
weight of a compound represented by general formula (II):
##STR00023## (wherein R.sup.3 and R.sup.4 are each independently an
alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8
carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an
alkenyloxy group of 2 to 8 carbon atoms; Z.sup.3 and Z.sup.4 are
each independently a single bond, --CH.dbd.CH--, --C.ident.C--,
--CH.sub.2CH.sub.2--, --(CH.sub.2).sub.4--, --COO--, --OCO--,
--OCH.sub.2--, --CH.sub.2O--, --OCF.sub.2--, or --CF.sub.2O--; B
and C are each independently optionally fluorinated 1,4-phenylene
or trans-1,4-cyclohexylene; and m and n are each independently an
integer of 0 to 4, wherein m+n=1 to 4), the curable resin
composition comprising a compound containing at least one epoxy
group per molecule and having a weight average molecular weight of
300 to 10,000.
2. The liquid crystal display device according to claim 1, wherein
the curable resin composition further comprises a thermal curing
agent.
3. The liquid crystal display device according to claim 1, wherein
the curable resin composition further comprises a silane coupling
agent.
4. The liquid crystal display device according to claim 1, wherein
the curable resin composition further comprises a filler.
5. The liquid crystal display device according to claim 1, wherein
the curable resin composition further comprises resin
particles.
6. The liquid crystal display device according to claim 1, wherein
the curable resin composition has a hydrogen-bonding functional
group value of 1.times.10.sup.4 to 5.times.10.sup.2 mol/g.
7. The liquid crystal display device according to claim 1, wherein
the compound containing at least one epoxy group per molecule and
having a weight average molecular weight of 300 to 10,000 further
contains at least one ethylenically unsaturated bond per
molecule.
8. The liquid crystal display device according to claim 7, wherein
the compound containing at least one epoxy group per molecule and
having a weight average molecular weight of 300 to 10,000 contains
at least one (meth)acrylic group per molecule.
9. The liquid crystal display device according to claim 8, wherein
the compound containing at least one (meth)acrylic group and at
least one epoxy group per molecule is a (meth)acrylic-modified
epoxy resin and/or a urethane-modified (meth)acrylic epoxy
resin.
10. The liquid crystal display device according to claim 1, wherein
the curable resin composition further comprises a compound
containing an ethylenically unsaturated bond.
11. The liquid crystal display device according to claim 10,
wherein the curable resin composition comprises a compound
containing a (meth)acryloyloxy group.
12. The liquid crystal display device according to claim 7, wherein
the curable resin composition has a carbon-carbon double bond
content of 1.times.10.sup.-3 to 5.times.10.sup.-3 mol/g.
13. The liquid crystal display device according to claim 8, wherein
the curable resin composition has an epoxy-to-(meth)acrylic
equivalent ratio of 15:85 to 95:5.
14. The liquid crystal display device according to claim 1, wherein
the liquid crystal composition further comprises a compound
represented by general formula (III): ##STR00024## (wherein R.sup.7
and R.sup.8 are each independently an alkyl group of 1 to 8 carbon
atoms, an alkenyl group of 2 to 8 carbon atoms, an alkoxy group of
1 to 8 carbon atoms, or an alkenyloxy group of 2 to 8 carbon atoms;
D, E, and F are each independently optionally fluorinated
1,4-phenylene or trans-1,4-cyclohexylene; Z.sup.2 is a single bond,
--OCH.sub.2--, --OCO--, --CH.sub.2O--, or --COO--; and n is 0, 1,
or 2, with the proviso that compounds represented by general
formulas (I), (II-1), and (II-2) are excluded).
15. The liquid crystal display device according to claim 1, wherein
the liquid crystal composition comprises at least one compound
represented by general formula (I) wherein A is
trans-1,4-cyclohexylene and at least one compound represented by
general formula (I) wherein A is 1,4-phenylene.
16. The liquid crystal display device according to claim 1, wherein
the liquid crystal composition comprises a compound represented by
general formula (II-1) and/or a compound represented by general
formula (II-2): ##STR00025## (wherein R.sup.3 and R.sup.4 are each
independently an alkyl group of 1 to 8 carbon atoms, an alkenyl
group of 2 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon
atoms, or an alkenyloxy group of 2 to 8 carbon atoms; Z.sup.5 and
Z.sup.6 are each independently a single bond, --CH.dbd.CH--,
--C.ident.C--, --CH.sub.2CH.sub.2--, --(CH.sub.2).sub.4--, --COO--,
--OCO--, --OCH.sub.2--, --CH.sub.2O--, --OCF.sub.2--, or
--CF.sub.2O--; and m1, m2, and n2 are each independently 0 or
1).
17. The liquid crystal display device according to claim 1, wherein
the liquid crystal composition has a rotational viscosity of 150 or
less, a refractive index anisotropy of 0.08 to 0.13, and a Z of
13,000 or less, wherein Z is represented by the following equation:
Z=.gamma.1/.DELTA.n.sup.2 [Math. 1] wherein .gamma.1 is the
rotational viscosity, and .DELTA.n is the refractive index
anisotropy.
18. The liquid crystal display device according to claim 1, wherein
the liquid crystal composition has an upper nematic liquid crystal
phase temperature limit of 60.degree. C. to 120.degree. C., a lower
nematic liquid crystal phase temperature limit of -20.degree. C. or
lower, and a difference between the upper and lower nematic liquid
crystal phase temperature limits of 100 to 150.
19. The liquid crystal display device according to claim 1, wherein
the liquid crystal composition has a resistivity of 10.sup.12
.OMEGA.m or more.
20. The liquid crystal display device according to claim 1, wherein
the liquid crystal layer comprises a polymer of the liquid crystal
composition, the liquid crystal composition further comprising a
polymerizable compound represented by general formula (V):
##STR00026## (wherein X.sup.1 and X.sup.2 are each independently
hydrogen or methyl; Sp.sup.1 and Sp.sup.2 are each independently a
single bond, an alkylene group of 1 to 8 carbon atoms, or
--O--(CH.sub.2).sub.s-- (wherein s is an integer of 2 to 7, and the
oxygen atom is attached to the aromatic ring); Z.sup.1 is
--OCH.sub.2--, --CH.sub.2O--, --COO--, --OCO--, --CF.sub.2O--,
--OCF.sub.2--, --CH.sub.2CH.sub.2--, --CF.sub.2CF.sub.2--,
--CH.dbd.CH--COO--, --CH.dbd.CH--OCO--, --COO--CH.dbd.CH--,
--OCO--CH.dbd.CH--, --COO--CH.sub.2CH.sub.2--,
--OCO--CH.sub.2CH.sub.2--, --CH.sub.2CH.sub.2--COO--,
--CH.sub.2CH.sub.2--OCO--, --COO--CH.sub.2--, --OCO--CH.sub.2--,
--CH.sub.2--COO--, --CH.sub.2--OCO--, --CY.sup.1.dbd.CY.sup.2--
(wherein Y.sup.1 and Y.sup.2 are each independently fluorine or
hydrogen), --C.dbd.C--, or a single bond; C is 1,4-phenylene,
trans-1,4-cyclohexylene, or a single bond; and any hydrogen atom in
any 1,4-phenylene group in the formula is optionally replaced with
fluorine).
21. The liquid crystal display device according to claim 20,
wherein C and Z.sup.1 in general formula (V) are single bonds.
Description
TECHNICAL FIELD
[0001] The present invention relates to liquid crystal display
devices.
BACKGROUND ART
[0002] Liquid crystal display devices are used in various products,
including clocks, calculators, household electrical appliances,
measuring instruments, automotive instrument panels, word
processors, electronic organizers, printers, computers, and
televisions. Typical types of liquid crystal display devices
include twisted nematic (TN), super-twisted nematic (STN), dynamic
scattering (DS), guest-host (GH), in-plane switching (IPS),
optically compensated birefringence (OCB), electrically controlled
birefringence (ECB), vertically aligned (VA), color
super-homeotropic (CSH), and ferroelectric liquid crystal (FLC)
display devices. Whereas conventional liquid crystal display
devices are statically driven, multiplexed liquid crystal display
devices are now in widespread use, including passive-matrix display
devices and, more recently, active-matrix (AM) display devices,
which are driven by elements such as thin-film transistors (TFTs)
and thin-film diodes (TFDs).
[0003] One of the widely used methods for manufacturing liquid
crystal display devices is one-drop filling using photocurable,
thermally curable sealants. This method begins by forming a
rectangular seal pattern on one of two transparent substrates
having electrodes thereon by dispensing or screen printing. Small
droplets of liquid crystal are then dispensed over the entire area
within the frame pattern of the uncured sealant on the transparent
substrate, immediately followed by laminating the other transparent
substrate and pre-curing the sealant by exposure to UV radiation.
The sealant is then post-cured by heating during the annealing of
the liquid crystal to produce a liquid crystal display device. The
substrates can be laminated together under reduced pressure, which
allows the liquid crystal display device to be significantly
efficiently manufactured.
[0004] However, if a photocurable, thermally curable sealant is
used in a small liquid crystal display panel, a seal pattern formed
of the sealant overlaps complicated metal wiring and a black
matrix. This leaves an unexposed area that has not been exposed to
light for pre-curing. In this area, the uncured sealant may
dissolve into and contaminate the liquid crystal during the process
from light exposure to thermal curing. Recent liquid crystal
display panels for low-power applications such as mobile
applications tend to include liquid crystals with low driving
voltages (low-voltage liquid crystals). Since low-voltage liquid
crystals have high dielectric anisotropy, they have a problem in
that they are readily contaminated with residues such as unreacted
polymerization initiator and curing agent, ionic impurities such as
chlorine, and other impurities such as silane coupling agents
present in the sealant. These impurities disturb the alignment and
decrease the voltage holding ratio over time.
[0005] Accordingly, thermally curable sealants for one-drop filling
that require no pre-curing by light exposure have been proposed.
However, conventional thermally curable sealants have a problem in
that the viscosity of the resin used as a raw material decreases
upon heating. This results in partial deformation of the seal
pattern and dissolution of the sealant components into the liquid
crystal and thus decreases the electrical characteristics of the
liquid crystal display device.
[0006] To reduce the dissolution of the sealant components into the
liquid crystal material, it has been proposed to increase the
softening point of the epoxy resin present in the sealant to reduce
the contamination of the liquid crystal material due to contact
with uncured sealant, thereby reducing color unevenness (PTL
1).
[0007] Although epoxy resins generally have high adhesion, they
tend to contaminate liquid crystal materials. One solution to this
problem is to reduce the contamination of a liquid crystal material
by acrylic modification. This technique is expected to reduce the
contamination of the liquid crystal material while improving the
adhesion. However, acrylic modification may decrease the thermal
curability and may thus result in contamination of the liquid
crystal material due to dissolution of the sealant components.
Accordingly, it has also been proposed to add a tertiary amine,
such as imidazole, for curing the acrylic component while adding a
small amount of epoxy resin, thereby thermally curing the acrylic
resin through the interaction with the epoxy resin (PTL 2).
[0008] Conventional thermally curable sealants also have a problem
in that the viscosity of the resin used as a raw material decreases
upon heating. This results in partial deformation of the seal
pattern and leakage of the liquid crystal outside the seal pattern.
Accordingly, a composition with improved curability without a
decrease in adhesion to substrates has been proposed (PTL 3).
[0009] However, the foregoing proposals assume common liquid
crystal materials and focus only on the compositions of sealants;
that is, they are intended to avoid the problems by modifying the
compositions of sealants. These proposals often fail to achieve
good display characteristics when applied to specific liquid
crystal display devices. In particular, these proposals are not
sufficiently effective in reducing image-sticking of liquid crystal
display devices.
CITATION LIST
Patent Literature
[0010] PTL 1: Japanese Unexamined Patent Application Publication
No. 2006-23582
[0011] PTL 2: Japanese Unexamined Patent Application Publication
No. 2008-116825
[0012] PTL 3: Japanese Unexamined Patent Application Publication
No. 2009-175180
SUMMARY OF INVENTION
Technical Problem
[0013] The present invention focuses on the interaction between the
compositions of liquid crystal materials and sealants, which has
not been sufficiently explored in the art, and proposes a
combination of a liquid crystal composition and a sealant
composition that provides a liquid crystal display device with
improved characteristics such as reduced image-sticking.
[0014] Specifically, the present invention provides a liquid
crystal display device including a particular liquid crystal
composition and a cured product of a particular curable resin
composition serving as a sealant. This liquid crystal display
device has a practical liquid crystal layer temperature limit, a
large absolute value of dielectric anisotropy (.DELTA..di-elect
cons.), a low viscosity, and a suitable refractive index anisotropy
(.DELTA.n) and does not suffer from a decrease in the voltage
holding ratio (VHR) of the liquid crystal layer or the problem of
display defects such as white spots, alignment unevenness, and
image-sticking.
Solution to Problem
[0015] To solve the foregoing problems, the inventors have
conducted extensive research on various combinations of curable
resin compositions for sealants and liquid crystal materials for
liquid crystal layers. As a result, the inventors have discovered
that a liquid crystal display device including a liquid crystal
material having a particular structure and a cured product of a
particular curable resin composition serving as a sealant does not
suffer from a decrease in the voltage holding ratio (VHR) of the
liquid crystal layer or the problem of display defects such as
white spots, alignment unevenness, and image-sticking. This
discovery has led to the present invention.
[0016] Specifically, the present invention provides a liquid
crystal display device including a first substrate, a second
substrate, a liquid crystal layer containing a liquid crystal
composition between the first and second substrates, and a sealant
joining together the first and second substrates. The sealant is a
cured product of a thermally curable resin composition. The liquid
crystal composition contains 10% to 50% by weight of a compound
represented by general formula (I).
##STR00001##
[0017] In the formula, R.sup.1 and R.sup.2 are each independently
an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8
carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an
alkenyloxy group of 2 to 8 carbon atoms; and A is 1,4-phenylene or
trans-1,4-cyclohexylene. The liquid crystal composition further
contains 35% to 80% by weight of a compound represented by general
formula (II).
##STR00002##
[0018] In the formula, R.sup.3 and R.sup.4 are each independently
an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8
carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an
alkenyloxy group of 2 to 8 carbon atoms; Z.sup.3 and Z.sup.4 are
each independently a single bond, --CH.dbd.CH--, --C.dbd.C--,
--CH.sub.2CH.sub.2--, --(CH.sub.2).sub.4--, --COO--, --OCO--,
--OCH.sub.2--, --CH.sub.2O--, --OCF.sub.2--, or --CF.sub.2O--; B
and C are each independently optionally fluorinated 1,4-phenylene
or trans-1,4-cyclohexylene; and m and n are each independently an
integer of 0 to 4, where m+n=1 to 4. The curable resin composition
contains a compound containing at least one epoxy group per
molecule and having a weight average molecular weight of 300 to
10,000.
Advantageous Effects of Invention
[0019] The liquid crystal display device according to the present
invention, which includes a particular liquid crystal composition
and a cured product of a particular curable resin composition
serving as a sealant, has a practical liquid crystal layer
temperature limit, a large absolute value of dielectric anisotropy
(.DELTA..di-elect cons.), a low viscosity, and a suitable
refractive index anisotropy (.DELTA.n) and does not suffer from a
decrease in the voltage holding ratio (VHR) of the liquid crystal
layer or display defects such as white spots, alignment unevenness,
and image-sticking.
BRIEF DESCRIPTION OF DRAWINGS
[0020] FIG. 1 is a plan view of a liquid crystal display device
according to the present invention.
[0021] FIG. 2 is an enlarged view of the liquid crystal display
device according to the present invention.
REFERENCE SIGNS LIST
[0022] 1 substrate [0023] 2 sealant [0024] 3 liquid crystal [0025]
4 driver [0026] 5 wiring line from pixel electrode [0027] 6
overcoat layer [0028] 7 pixel electrode or wiring line [0029] 8
alignment layer
DESCRIPTION OF EMBODIMENTS
[0030] FIG. 1 is a plan view of a liquid crystal display device
according to the present invention, where details such as pixel
electrodes, TFTs, and wiring lines are not shown. The upper view of
FIG. 2 is a partial enlarged view of the plan view, showing that
wiring lines extend under a sealant from pixel electrodes to a
driver. The lower view of FIG. 2 is a sectional view of the upper
view of FIG. 2. The sealant contacts a liquid crystal and an
alignment layer. Although not all situations are shown in the
drawings, the sealant or the liquid crystal may contact the wiring
lines or an overcoat layer depending on the position of the
sealant.
Liquid Crystal Layer
[0031] The liquid crystal layer of the liquid crystal display
device according to the present invention is formed of a liquid
crystal composition containing 10% to 50% by weight of a compound
represented by general formula (I).
##STR00003##
[0032] In the formula, R.sup.1 and R.sup.2 are each independently
an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8
carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an
alkenyloxy group of 2 to 8 carbon atoms; and A is 1,4-phenylene or
trans-1,4-cyclohexylene. The liquid crystal composition further
contains 35% to 80% by weight of a compound represented by general
formula (II):
##STR00004##
[0033] In the formula, R.sup.3 and R.sup.4 are each independently
an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8
carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an
alkenyloxy group of 2 to 8 carbon atoms; Z.sup.3 and Z.sup.4 are
each independently a single bond, --CH.dbd.CH--, --C.dbd.C--,
--CH.sub.2CH.sub.2--, --(CH.sub.2).sub.4--, --COO--, --OCO--,
--OCH.sub.2--, --CH.sub.2O--, --OCF.sub.2--, or --CF.sub.2O--; B
and C are each independently optionally fluorinated 1,4-phenylene
or trans-1,4-cyclohexylene; and m and n are each independently an
integer of 0 to 4, wherein m+n=1 to 4.
[0034] The compound represented by general formula (I) is present
in the liquid crystal layer of the liquid crystal display device
according to the present invention in an amount of 10% to 50% by
weight, preferably 15% to 48% by weight, more preferably 20% to 46%
by weight.
[0035] In general formula (I), R.sup.1 and R.sup.2 are each
independently an alkyl group of 1 to 8 carbon atoms, an alkenyl
group of 2 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon
atoms, or an alkenyloxy group of 2 to 8 carbon atoms. If A is
trans-1,4-cyclohexylene, R.sup.1 and R.sup.2 are each preferably an
alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5
carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or an
alkenyloxy group of 2 to 5 carbon atoms, more preferably an alkyl
group of 2 to 5 carbon atoms, an alkenyl group of 2 to 4 carbon
atoms, an alkoxy group of 1 to 4 carbon atoms, or an alkenyloxy
group of 2 to 4 carbon atoms. R.sup.1 is preferably an alkyl group,
more preferably an alkyl group of 2, 3, or 4 carbon atoms. If
R.sup.1 is an alkyl group of 3 carbon atoms, R.sup.2 is preferably
an alkyl group of 2, 4, or 5 carbon atoms or an alkenyl group of 2
or 3 carbon atoms, more preferably an alkyl group of 2 carbon
atoms.
[0036] If A is 1,4-phenylene, R.sup.1 and R.sup.2 are each
preferably an alkyl group of 1 to 5 carbon atoms, an alkenyl group
of 4 or 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or
an alkenyloxy group of 3 to 5 carbon atoms, more preferably an
alkyl group of 2 to 5 carbon atoms, an alkenyl group of 4 or 5
carbon atoms, an alkoxy group of 1 to 4 carbon atoms, or an
alkenyloxy group of 2 to 4 carbon atoms. R.sup.1 is preferably an
alkyl group, more preferably an alkyl group of 1, 3, or 5 carbon
atoms. R.sup.2 is preferably an alkoxy group of 1 or 2 carbon
atoms.
[0037] Preferably, compounds represented by general formula (I)
where at least one of R.sup.1 and R.sup.2 is an alkyl group of 3 to
5 carbon atoms are present in an amount of 50% by weight or more,
more preferably 70% by weight or more, even more preferably 80% by
weight or more, of all the compounds represented by general formula
(I). Preferably, compounds represented by general formula (I) where
at least one of R.sup.1 and R.sup.2 is an alkyl group of 3 carbon
atoms are present in an amount of 50% by weight or more, more
preferably 70% by weight or more, even more preferably 80% by
weight or more, most preferably 100% by weight, of all the
compounds represented by general formula (I).
[0038] The liquid crystal composition may contain one or more
compounds represented by general formula (I), preferably at least
one compound where A is trans-1,4-cyclohexylene and at least one
compound where A is 1,4-phenylene.
[0039] Preferably, compounds represented by general formula (I)
where A is trans-1,4-cyclohexylene are present in an amount of 50%
by weight or more, more preferably 70% by weight or more, even more
preferably 80% by weight or more, of all the compounds represented
by general formula (I).
[0040] Specific preferred compounds represented by general formula
(I) include compounds represented by general formulas (Ia) to (Ik)
below.
##STR00005##
[0041] In the formulas, R.sup.1 and R.sup.2 are each independently
an alkyl group of 1 to 5 carbon atoms or an alkoxy group of 1 to 5
carbon atoms, preferably as defined for R.sup.1 and R.sup.2,
respectively, in general formula (I).
[0042] Preferred among general formulas (Ia) to (Ik) are general
formulas (Ia), (Ib), (Ic), and (Ig), more preferably general
formulas (Ia), (Ib), and (Ic), even more preferably general
formulas (Ia) and (Ib). General formulas (Ib) and (Ic) are
preferred to achieve a faster response time, and it is more
preferred to use a combination of general formulas (Ib) and (Ic).
General formula (Ia) is preferred to achieve a higher
reliability.
[0043] With these points in mind, compounds represented by general
formulas (Ia), (Ib), and (Ic) are preferably present in an amount
of 80% by weight or more, more preferably 90% by weight or more,
even more preferably 95% by weight or more, most preferably 100% by
weight, of all the compounds represented by general formula (I).
Preferably, compounds represented by general formula (Ia) are
present in an amount of 65% to 100% by weight of all the compounds
represented by general formula (I), and compounds represented by
general formulas (Ib) and (Ic) are present in an amount of 0% to
35% by weight of all the compounds represented by general formula
(I). Also preferably, compounds represented by general formula (Ia)
are present in an amount of 0% to 10% by weight of all the
compounds represented by general formula (I), and compounds
represented by general formulas (Ib) and (Ic) are present in an
amount of 90% to 100% by weight of all the compounds represented by
general formula (I).
[0044] The compound represented by general formula (II) is present
in the liquid crystal layer of the liquid crystal display device
according to the present invention in an amount of 35% to 80% by
weight, preferably 40% to 75% by weight, more preferably 45% to 70%
by weight.
[0045] In general formula (II), R.sup.3 is an alkyl group of 1 to 8
carbon atoms, an alkenyl group of 2 to 8 carbon atoms, an alkoxy
group of 1 to 8 carbon atoms, or an alkenyloxy group of 2 to 8
carbon atoms. Preferably, R.sup.3 is an alkyl group of 1 to 5
carbon atoms or an alkenyl group of 2 to 5 carbon atoms, more
preferably an alkyl group of 2 to 5 carbon atoms or an alkenyl
group of 2 to 4 carbon atoms, even more preferably an alkyl group
of 3 to 5 carbon atoms or an alkenyl group of 2 or 3 carbon atoms,
still more preferably an alkyl group of 2 or 3 carbon atoms or an
alkenyl group of 2 carbon atoms, most preferably an alkyl group of
2 or 3 carbon atoms.
[0046] R.sup.4 is an alkyl group of 1 to 8 carbon atoms, an alkenyl
group of 4 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon
atoms, or an alkenyloxy group of 3 to 8 carbon atoms. Preferably,
R.sup.4 is an alkyl group of 1 to 5 carbon atoms or an alkoxy group
of 1 to 5 carbon atoms, more preferably an alkyl group of 1 to 3
carbon atoms or an alkoxy group of 1 to 4 carbon atoms, even more
preferably an alkoxy group of 2 to 4 carbon atoms. Z.sup.3 and
Z.sup.4 are each independently a single bond, --CH.dbd.CH--,
--C.dbd.C--, --CH.sub.2CH.sub.2--, --(CH.sub.2).sub.4--, --COO--,
--OCO--, --OCH.sub.2--, --CH.sub.2O--, --OCF.sub.2--, or
--CF.sub.2O--. Preferably, Z.sup.3 and Z.sup.4 are each a single
bond, --CH.sub.2CH.sub.2--, --COO--, --OCH.sub.2--, --CH.sub.2O--,
--OCF.sub.2--, or --CF.sub.2O--, more preferably a single bond or
--CH.sub.2O--.
[0047] m and n are preferably each independently an integer of 0 to
3, more preferably an integer of 0 to 2, and m+n is preferably 1 to
3, more preferably 1 or 2.
[0048] The liquid crystal layer of the liquid crystal display
device according to the present invention may contain three to ten,
preferably four to nine, even more preferably five to eight,
compounds represented by general formula (II).
[0049] Preferred compounds represented by general formula (II)
include compounds represented by general formulas (II-1) and (II-2)
below.
##STR00006##
[0050] In the formulas, R.sup.3 and R.sup.4 are each independently
an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8
carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an
alkenyloxy group of 2 to 8 carbon atoms; Z.sup.5 and Z.sup.6 are
each independently a single bond, --CH.dbd.CH--, --C.dbd.C--,
--CH.sub.2CH.sub.2--, --(CH.sub.2).sub.4--, --COO--, --OCO--,
--OCH.sub.2--, --CH.sub.2O--, --OCF.sub.2--, or --CF.sub.2O--; and
m1, m2, and n2 are each independently 0 or 1.
[0051] In general formula (II-1), R.sup.3 is preferably an alkyl
group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon
atoms, more preferably an alkyl group of 2 to 5 carbon atoms or an
alkenyl group of 2 to 4 carbon atoms, even more preferably an alkyl
group of 3 to 5 carbon atoms or an alkenyl group of 2 carbon atoms,
still more preferably an alkyl group of 3 carbon atoms. R.sup.4 is
preferably an alkyl group of 1 to 5 carbon atoms or an alkoxy group
of 1 to 5 carbon atoms, more preferably an alkyl group of 1 to 3
carbon atoms or an alkoxy group of 1 to 3 carbon atoms, even more
preferably an alkyl group of 3 carbon atoms or an alkoxy group of 2
carbon atoms, still more preferably an alkoxy group of 2 carbon
atoms. Z.sup.5 is preferably a single bond, --CH.sub.2CH.sub.2--,
--COO--, --OCH.sub.2--, --CH.sub.2O--, --OCF.sub.2--, or
--CF.sub.2O--, more preferably a single bond or --CH.sub.2O--.
[0052] The compound represented by general formula (II-1) is
preferably present in the liquid crystal layer of the liquid
crystal display device according to the present invention in an
amount of 15% to 60% by weight, more preferably 17% to 50% by
weight, even more preferably 18% to 40% by weight, still more
preferably 19% to 30% by weight.
[0053] The liquid crystal layer of the liquid crystal display
device according to the present invention may contain one or more,
preferably one to six, even more preferably two to five, still more
preferably three or four, compounds represented by general formula
(II-1).
[0054] In general formula (II-2), R.sup.3 is preferably an alkyl
group of 1 to 5 carbon atoms or an alkenyl group of 2 to 5 carbon
atoms, more preferably an alkyl group of 2 to 5 carbon atoms or an
alkenyl group of 2 to 4 carbon atoms, even more preferably an alkyl
group of 3 to 5 carbon atoms or an alkenyl group of 2 carbon atoms,
still more preferably an alkyl group of 2 or 3 carbon atoms.
R.sup.4 is preferably an alkyl group of 1 to 5 carbon atoms or an
alkoxy group of 1 to 5 carbon atoms, more preferably an alkyl group
of 1 to 3 carbon atoms or an alkoxy group of 1 to 3 carbon atoms,
even more preferably an alkyl group of 3 carbon atoms or an alkoxy
group of 2 carbon atoms. Z.sup.6 is preferably a single bond,
--CH.sub.2CH.sub.2--, --COO--, --OCH.sub.2--, --CH.sub.2O--,
--OCF.sub.2--, or --CF.sub.2O--, more preferably a single bond or
--CH.sub.2O--.
[0055] The compound represented by general formula (II-2) is
preferably present in the liquid crystal layer of the liquid
crystal display device according to the present invention in an
amount of 10% to 50% by weight, more preferably 15% to 45% by
weight, even more preferably 20% to 40% by weight, still more
preferably 25% to 35% by weight.
[0056] The liquid crystal layer of the liquid crystal display
device according to the present invention may contain one or more,
preferably one to six, even more preferably two to five, still more
preferably three or four, compounds represented by general formula
(II-2).
[0057] Specific preferred compounds represented by general formula
(II-1) include compounds represented by general formulas (II-1a) to
(II-1d) below.
##STR00007##
[0058] In the formulas, R.sup.3 is an alkyl group of 1 to 5 carbon
atoms or an alkenyl group of 2 to 5 carbon atoms, and R.sup.4a is
an alkyl group of 1 to 5 carbon atoms.
[0059] In general formulas (II-1a) and (II-1c), R.sup.3 is
preferably as defined in general formula (II-1). R.sup.4a is
preferably an alkyl group of 1 to 3 carbon atoms, more preferably
an alkyl group of 1 or 2 carbon atoms, even more preferably an
alkyl group of 2 carbon atoms.
[0060] In general formulas (II-1b) and (II-1d), R.sup.3 is
preferably as defined in general formula (II-1). R.sup.4a is
preferably an alkyl group of 1 to 3 carbon atoms, more preferably
an alkyl group of 1 or 3 carbon atoms, even more preferably an
alkyl group of 3 carbon atoms.
[0061] Among general formulas (II-1a) to (II-1d), general formulas
(II-1a) and (II-1c) are preferred, more preferably general formula
(II-1a), to achieve a larger absolute value of dielectric
anisotropy.
[0062] The liquid crystal layer of the liquid crystal display
device according to the present invention preferably contains one
or more, more preferably one or two, compounds represented by any
of general formulas (II-1a) to (II-1d), even more preferably one or
two compounds represented by general formula (II-1a).
[0063] Other specific preferred compounds represented by general
formula (II-1) include compounds represented by general formulas
(II-1e) to (II-1h) below.
##STR00008##
[0064] In the formulas, R.sup.3 is an alkyl group of 1 to 5 carbon
atoms or an alkenyl group of 2 to 5 carbon atoms, and R.sup.4b is
an alkyl group of 1 to 5 carbon atoms.
[0065] In general formulas (II-1e) and (II-1g), R.sup.3 is
preferably as defined in general formula (II-1). R.sup.4b is
preferably an alkyl group of 1 to 3 carbon atoms, more preferably
an alkyl group of 1 or 2 carbon atoms, even more preferably an
alkyl group of 2 carbon atoms.
[0066] In general formulas (II-1f) and (II-1h), R.sup.3 is
preferably as defined in general formula (II-1). R.sup.4b is
preferably an alkyl group of 1 to 3 carbon atoms, more preferably
an alkyl group of 1 or 3 carbon atoms, even more preferably an
alkyl group of 3 carbon atoms.
[0067] Among general formulas (II-1e) to (II-1h), general formulas
(II-1e) and (II-1g) are preferred to achieve a larger absolute
value of dielectric anisotropy.
[0068] Specific preferred compounds represented by general formula
(II-2) include compounds represented by general formulas (II-2a) to
(II-2d) below.
##STR00009##
[0069] In the formulas, R.sup.3 is an alkyl group of 1 to 5 carbon
atoms or an alkenyl group of 2 to 5 carbon atoms, and R.sup.4c is
an alkyl group of 1 to 5 carbon atoms. Preferably, R.sup.3 and
R.sup.4c are as defined for R.sup.3 and R.sup.4, respectively, in
general formula (II-2).
[0070] In general formulas (II-2a) and (II-2c), R.sup.3 is
preferably as defined in general formula (II-2). R.sup.4c is
preferably an alkyl group of 1 to 3 carbon atoms, more preferably
an alkyl group of 1 or 2 carbon atoms, even more preferably an
alkyl group of 2 carbon atoms.
[0071] In general formulas (II-2b) and (II-2d), R.sup.3 is
preferably as defined in general formula (II-2). R.sup.4c is
preferably an alkyl group of 1 to 3 carbon atoms, more preferably
an alkyl group of 1 or 3 carbon atoms, even more preferably an
alkyl group of 3 carbon atoms.
[0072] Among general formulas (II-2a) to (II-2d), general formula
(II-2a) and (II-2c) are preferred, more preferably general formula
(II-2a), to achieve a larger absolute value of dielectric
anisotropy.
[0073] Other specific preferred compounds represented by general
formula (II-2) include compounds represented by general formulas
(II-2e) to (II-2j) below.
##STR00010##
[0074] In the formulas, R.sup.3 is an alkyl group of 1 to 5 carbon
atoms or an alkenyl group of 2 to 5 carbon atoms, and R.sup.4d is
an alkyl group of 1 to 5 carbon atoms. Preferably, R.sup.3 and
R.sup.4d are as defined for R.sup.3 and R.sup.4, respectively, in
general formula (II-2).
[0075] In general formulas (II-2e), (II-2g), and (II-2i), R.sup.3
is preferably as defined in general formula (II-2). R.sup.4d is
preferably an alkyl group of 1 to 3 carbon atoms, more preferably
an alkyl group of 1 or 2 carbon atoms, even more preferably an
alkyl group of 2 carbon atoms.
[0076] In general formulas (II-2f), (II-2h), and (II-2j), R.sup.3
is preferably as defined in general formula (II-2). R.sup.4d is
preferably an alkyl group of 1 to 3 carbon atoms, more preferably
an alkyl group of 1 or 3 carbon atoms, even more preferably an
alkyl group of 2 carbon atoms.
[0077] Among general formulas (II-2e) to (II-2i), general formulas
(II-2e) and (II-2h) are preferred.
[0078] The compounds represented by general formula (I) and (II)
are preferably present in the liquid crystal layer of the liquid
crystal display device according to the present invention in a
total amount of 75% to 100% by weight, more preferably 80% to 100%
by weight, even more preferably 85% to 100% by weight, still more
preferably 90% to 100% by weight, most preferably 95% to 100% by
weight.
[0079] The liquid crystal layer of the liquid crystal display
device according to the present invention may further contain a
compound represented by general formula (III).
##STR00011##
[0080] In the formula, R.sup.7 and R.sup.8 are each independently
an alkyl group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8
carbon atoms, an alkoxy group of 1 to 8 carbon atoms, or an
alkenyloxy group of 2 to 8 carbon atoms; D, E, and F are each
independently optionally fluorinated 1,4-phenylene or
trans-1,4-cyclohexylene; Z.sup.2 is a single bond, --OCH.sub.2--,
--OCO--, --CH.sub.2O--, --COO--, or --OCO--; and n is 0, 1, or 2,
with the proviso that compounds represented by general formulas
(I), (II-1), and (II-2) are excluded.
[0081] The compound represented by general formula (III) is
preferably present in an amount of 1% to 20%, more preferably 2% to
15%, even more preferably 4% to 10%.
[0082] In general formula (III), R.sup.7 is an alkyl group of 1 to
8 carbon atoms, an alkenyl group of 2 to 8 carbon atoms, an alkoxy
group of 1 to 8 carbon atoms, or an alkenyloxy group of 2 to 8
carbon atoms. If D is trans-1,4-cyclohexylene, R.sup.7 is
preferably an alkyl group of 1 to 5 carbon atoms or an alkenyl
group of 2 to 5 carbon atoms, more preferably an alkyl group of 2
to 5 carbon atoms or an alkenyl group of 2 to 4 carbon atoms, even
more preferably an alkyl group of 3 to 5 carbon atoms or an alkenyl
group of 2 or 3 carbon atoms, still more preferably an alkyl group
of 3 carbon atoms. If D is optionally fluorinated 1,4-phenylene,
R.sup.7 is preferably an alkyl group of 1 to 5 carbon atoms or an
alkenyl group of 4 or 5 carbon atoms, more preferably an alkyl
group of 2 to 5 carbon atoms or an alkenyl group of 4 carbon atoms,
even more preferably an alkyl group of 2 to 4 carbon atoms.
[0083] R.sup.8 is an alkyl group of 1 to 8 carbon atoms, an alkenyl
group of 2 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon
atoms, or an alkenyloxy group of 3 to 8 carbon atoms. If F is
trans-1,4-cyclohexylene, R.sup.8 is preferably an alkyl group of 1
to 5 carbon atoms or an alkenyl group of 2 to 5 carbon atoms, more
preferably an alkyl group of 2 to 5 carbon atoms or an alkenyl
group of 2 to 4 carbon atoms, even more preferably an alkyl group
of 3 to 5 carbon atoms or an alkenyl group of 2 or 3 carbon atoms,
still more preferably an alkyl group of 3 carbon atoms. If F is
optionally fluorinated 1,4-phenylene, R.sup.8 is preferably an
alkyl group of 1 to 5 carbon atoms or an alkenyl group of 4 or 5
carbon atoms, more preferably an alkyl group of 2 to 5 carbon atoms
or an alkenyl group of 4 carbon atoms, even more preferably an
alkyl group of 2 to 4 carbon atoms.
[0084] If R.sup.7 or R.sup.8 is an alkenyl group and D or F to
which it is attached is optionally fluorinated 1,4-phenylene,
alkenyl groups of 4 or 5 carbon atoms having the following
structures are preferred.
##STR00012##
[0085] In the formulas, the right end is attached to the cyclic
structure. In this case, the alkenyl group of 4 carbon atoms is
more preferred.
[0086] D, E, and F are each independently optionally fluorinated
1,4-phenylene or trans-1,4-cyclohexylene, preferably
2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 1,4-phenylene,
or trans-1,4-cyclohexylene, more preferably 2-fluoro-1,4-phenylene,
2,3-difluoro-1,4-phenylene, or 1,4-phenylene, even more preferably
2,3-difluoro-1,4-phenylene or 1,4-phenylene. Z.sup.2 is a single
bond, --OCH.sub.2--, --OCO--, --CH.sub.2O--, or --COO--, preferably
a single bond, --CH.sub.2O--, or --COO--, more preferably a single
bond.
[0087] n is 0, 1, or 2, preferably 0 or 1. If Z.sup.2 is a
substituent, rather than a single bond, n is preferably 1.
[0088] Among compounds represented by general formula (III) where n
is 1, compounds represented by general formulas (III-1c) to
(III-1e) are preferred to achieve a larger negative dielectric
anisotropy, and general formulas (III-1f) to (III-1j) are preferred
to achieve a faster response time.
##STR00013##
[0089] In the formulas, R.sup.7 and R.sup.8 are each independently
an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5
carbon atoms, or an alkoxy group of 1 to 5 carbon atoms, preferably
as defined for R.sup.7 and R.sup.8, respectively, in general
formula (III).
[0090] Among compounds represented by general formula (III) where n
is 2, compounds represented by general formulas (III-2a) to
(III-2h) are preferred to achieve a larger negative dielectric
anisotropy, and general formulas (III-2j) to (III-2l) are preferred
to achieve a faster response time.
##STR00014## ##STR00015##
[0091] In the formulas, R.sup.7 and R.sup.8 are each independently
an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5
carbon atoms, or an alkoxy group of 1 to 5 carbon atoms, preferably
as defined for R.sup.7 and R.sup.8, respectively, in general
formula (III).
[0092] Among compounds represented by general formula (III) where n
is O, compounds represented by general formula (III-3b) are
preferred to achieve a faster response time.
##STR00016##
[0093] In the formula, R.sup.7 and R.sup.8 are each independently
an alkyl group of 1 to 5 carbon atoms, an alkenyl group of 2 to 5
carbon atoms, or an alkoxy group of 1 to 5 carbon atoms, preferably
as defined for R.sup.7 and R.sup.8, respectively, in general
formula (III).
[0094] R.sup.7 is preferably an alkyl group of 2 to 5 carbon atoms,
more preferably an alkyl group of 3 carbon atoms. R.sup.8 is
preferably an alkoxy group of 1 to 3 carbon atoms, more preferably
an alkoxy group of 2 carbon atoms.
[0095] The liquid crystal layer of the liquid crystal display
device according to the present invention can have a wide range of
nematic-isotropic liquid phase transition temperature (T.sub.ni).
Preferably, the liquid crystal layer has a nematic-isotropic liquid
phase transition temperature (T.sub.ni) of 60.degree. C. to
120.degree. C., more preferably 70.degree. C. to 100.degree. C.,
even more preferably 70.degree. C. to 85.degree. C.
[0096] The liquid crystal layer of the liquid crystal display
device according to the present invention preferably has a
dielectric anisotropy at 25.degree. C. of -2.0 to -6.0, more
preferably -2.5 to -5.0, even more preferably -2.5 to -4.0.
[0097] The liquid crystal layer of the liquid crystal display
device according to the present invention preferably has a
refractive index anisotropy at 25.degree. C. of 0.08 to 0.13, more
preferably 0.09 to 0.12. For small cell gaps, the liquid crystal
layer preferably has a refractive index anisotropy at 25.degree. C.
of 0.10 to 0.12. For large cell gaps, the liquid crystal layer
preferably has a refractive index anisotropy at 25.degree. C. of
0.08 to 0.10.
[0098] The liquid crystal layer of the liquid crystal display
device according to the present invention preferably has a
rotational viscosity (.gamma.1) of 150 or less, more preferably 130
or less, even more preferably 120 or less.
[0099] The liquid crystal layer of the liquid crystal display
device according to the present invention preferably has a
particular value of Z, which is a function of rotational viscosity
and refractive index anisotropy.
Z=.gamma.1/.DELTA.n.sup.2 [Math. 1]
[0100] In the equation, .gamma.1 is the rotational viscosity, and
.DELTA.n is the refractive index anisotropy. Z is preferably 13,000
or less, more preferably 12,000 or less, even more preferably
11,000 or less.
[0101] When used in an active-matrix display device, the liquid
crystal layer of the liquid crystal display device according to the
present invention has to have a resistivity of 10.sup.12 .OMEGA.m
or more, preferably 10.sup.13 .OMEGA.m, more preferably 10.sup.14
.OMEGA.m or more.
[0102] In addition to the compounds described above, the liquid
crystal layer of the liquid crystal display device according to the
present invention may contain other components depending on the
application, including common nematic, smectic, and cholesteric
liquid crystals, antioxidants, UV absorbers, and polymerizable
monomers.
[0103] A preferred polymerizable monomer is a difunctional monomer
represented by general formula (V).
##STR00017##
[0104] In the formula, X.sup.1 and X.sup.2 are each independently
hydrogen or methyl; Sp.sup.1 and Sp.sup.2 are each independently a
single bond, an alkylene group of 1 to 8 carbon atoms, or
--O--(CH.sub.2).sub.s-- (where s is an integer of 2 to 7, and the
oxygen atom is attached to the aromatic ring); Z is --OCH.sub.2--,
--CH.sub.2O--, --COO--, --OCO--, --CF.sub.2O--, --OCF.sub.2--,
--CH.sub.2CH.sub.2--, --CF.sub.2CF.sub.2--, --CH.dbd.CH--COO--,
--CH.dbd.CH--OCO--, --COO--CH.dbd.CH--, --OCO--CH.dbd.CH--,
--COO--CH.sub.2CH.sub.2--, --OCO--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2--COO--, --CH.sub.2CH.sub.2--OCO--,
--COO--CH.sub.2--, --OCO--CH.sub.2--, --CH.sub.2--COO--,
--CH.sub.2--OCO--, --CY.sup.1.dbd.CY.sup.2-- (where Y.sup.1 and
Y.sup.2 are each independently fluorine or hydrogen),
--C.ident.C--, or a single bond; C is 1,4-phenylene,
trans-1,4-cyclohexylene, or a single bond; and any hydrogen atom in
any 1,4-phenylene group in the formula is optionally replaced with
fluorine.
[0105] Preferred difunctional monomers include diacrylate
derivatives, where both X.sup.1 and X.sup.2 are hydrogen, and
dimethacrylate derivatives, where both X.sup.1 and X.sup.2 are
methyl. Also preferred are compounds where one of X.sup.1 and
X.sup.2 is hydrogen and the other is methyl. Diacrylate derivatives
have the highest rates of polymerization, dimethacrylate
derivatives have the lowest rates of polymerization, and
asymmetrical compounds have intermediate rates of polymerization,
of which any suitable compound may be used depending on the
application. Dimethacrylate derivatives are preferred for PSA
display devices.
[0106] Sp.sup.1 and Sp.sup.2 above are each independently a single
bond, an alkylene group of 1 to 8 carbon atoms, or
--O--(CH.sub.2).sub.s--. Compounds where at least one of Sp.sup.1
and Sp.sup.2 is a single bond are preferred for PSA display
devices, including those where both of Sp.sup.1 and Sp.sup.2 are
single bonds and those where one of Sp.sup.1 and Sp.sup.2 is a
single bond and the other is an alkylene group of 1 to 8 carbon
atoms or --O--(CH.sub.2).sub.s--. In this case, an alkyl group of 1
to 4 carbon atoms is preferred, and s is preferably 1 to 4.
[0107] Z.sup.1 is preferably --OCH.sub.2--, --CH.sub.2O--, --COO--,
--OCO--, --CF.sub.2O--, --OCF.sub.2--, --CH.sub.2CH.sub.2--,
--CF.sub.2CF.sub.2--, or a single bond, more preferably --COO--,
--OCO--, or a single bond, even more preferably a single bond.
[0108] C is 1,4-phenylene or trans-1,4-cyclohexylene where any
hydrogen atom is optionally replaced with fluorine, or a single
bond. Preferably, C is 1,4-phenylene or a single bond. If C is a
cyclic structure, rather than a single bond, Z.sup.1 is also
preferably a linking group, rather than a single bond. If C is a
single bond, Z.sup.1 is preferably a single bond.
[0109] With these points in mind, specific preferred cyclic
structures between Sp.sup.1 and Sp.sup.2 in general formula (V)
include the following structures.
[0110] If C in general formula (V) is a single bond, preferred
cyclic structures composed of two rings include those represented
by formulas (Va-1) to (Va-5) below, more preferably formulas (Va-1)
to (Va-3), even more preferably formula (Va-1).
##STR00018##
[0111] In the formulas, both ends are attached to Sp.sup.1 and
Sp.sup.2.
[0112] Polymerizable compounds having these backbones have optimal
anchoring force for PSA display devices after polymerization, which
results in good alignment with little or no display unevenness.
[0113] With the above in mind, preferred polymerizable monomers
include those represented by general formulas (V-1) to (V-4), most
preferably general formula (V-2).
##STR00019##
[0114] In the formulas, Sp.sup.2 is an alkylene group of 2 to 5
carbon atoms.
[0115] Although a polymerizable monomer, if used, polymerizes
without a polymerization initiator, a polymerization initiator may
be added to promote the polymerization. Examples of polymerization
initiators include benzoin ethers, benzophenones, acetophenones,
benzyl ketals, and acylphosphine oxides. A stabilizer may also be
added to improve the storage stability. Examples of stabilizers
that can be used include hydroquinones, hydroquinone monoalkyl
ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro
compounds, .beta.-naphthylamines, .beta.-naphthols, and nitroso
compounds.
[0116] The liquid crystal layer according to the present invention
is useful for liquid crystal display devices such as active-matrix
liquid crystal display devices (AM-LCDs), twisted nematic (TN)
liquid crystal display devices, super-twisted nematic liquid
crystal display devices (STN-LCDs), OCB-LCDs, and in-plane
switching liquid crystal display devices (IPS-LCDs). In particular,
the liquid crystal layer according to the present invention can be
used for AM-LCDs such as PSA, PSVA, VA, IPS, and ECB liquid crystal
display devices.
Sealant
[0117] The sealant used in the liquid crystal display device
according to the present invention is formed of a cured product of
a curable resin composition containing a compound containing at
least one epoxy group per molecule and having a weight average
molecular weight of 300 to 10,000.
[0118] Examples of compounds containing at least one epoxy group
per molecule include novolac epoxy resins and bisphenol epoxy
resins. Specific preferred examples include biphenyl epoxy resins,
naphthalene epoxy resins, tris(hydroxyphenyl)alkyl epoxy resins,
and tetrakis(hydroxyphenyl)alkyl epoxy resins. More specific
examples include bisphenol A epoxy resins, bisphenol E epoxy
resins, bisphenol F epoxy resins, bisphenol S epoxy resins,
2,2'-diallyl bisphenol A epoxy resins, hydrogenated bisphenol epoxy
resins, polyoxypropylene bisphenol A epoxy resins, propylene oxide
adducts of bisphenol A epoxy resins, resorcinol epoxy resins,
biphenyl epoxy resins, sulfide epoxy resins, diphenyl ether epoxy
resins, dicyclopentadiene epoxy resins, naphthalene epoxy resins,
phenol novolac epoxy resins, cresol novolac epoxy resins,
trisphenol novolac epoxy resins, dicyclopentadiene novolac epoxy
resins, biphenyl novolac epoxy resins, naphthalene phenol novolac
epoxy resins, glycidylamine epoxy resins, alkyl polyol epoxy
resins, rubber-modified epoxy resins, glycidyl esters, and
bisphenol A episulfide resins. Preferred among these are bisphenol
A epoxy resins, bisphenol E epoxy resins, bisphenol F epoxy resins,
resorcinol epoxy resins, phenol novolac epoxy resins, and diphenyl
ether epoxy resins.
[0119] Examples of commercially available epoxy compounds include
bisphenol A epoxy resins such as jER828EL, jER1004 (available from
Mitsubishi Chemical Corporation), and Epiclon 850-S (available from
DIC Corporation); bisphenol F epoxy resins such as jER806 and
jER4004 (available from Mitsubishi Chemical Corporation); bisphenol
E epoxy resins such as R-710; bisphenol S epoxy resins such as
Epiclon EXA1514 (available from DIC Corporation); 2,2'-diallyl
bisphenol A epoxy resins such as RE-810NM (available from Nippon
Kayaku Co., Ltd.); hydrogenated bisphenol epoxy resins such as
Epiclon EXA7015 (available from DIC Corporation); propylene oxide
adducts of bisphenol A epoxy resins such as EP-4000S (available
from Adeka Corporation); resorcinol epoxy resins such as EX-201
(available from Nagase ChemteX Corporation); biphenyl epoxy resins
such as jERYX-4000H (available from Mitsubishi Chemical
Corporation); sulfide epoxy resins such as YSLV-50TE (available
from Nippon Steel Chemical Co., Ltd.); biphenyl ether epoxy resins
such as YSLV-80DE (available from Nippon Steel Chemical Co., Ltd.);
dicyclopentadiene epoxy resins such as EP-4088S (available from
Adeka Corporation); naphthalene epoxy resins such as Epiclon HP4032
and Epiclon EXA-4700 (available from DIC Corporation); phenol
novolac epoxy resins such as Epiclon N-740, Epiclon N-770, Epiclon
N-775 (available from DIC Corporation), jER152, and jER154
(available from Mitsubishi Chemical Corporation); o-cresol novolac
epoxy resins such as Epiclon N-670-EXP-S (available from DIC
Corporation); cresol novolac epoxy resins such as Epiclon N660,
Epiclon N665, Epiclon N670, Epiclon N673, Epiclon N680, Epiclon
N695, Epiclon N665EXP, and Epiclon N672EXP (available from DIC
Corporation); dicyclopentadiene novolac epoxy resins such as
Epiclon HP7200 (available from DIC Corporation); biphenyl novolac
epoxy resins such as NC-3000P (available from Nippon Kayaku Co.,
Ltd.); naphthalene phenol novolac epoxy resins such as ESN-165S
(available from Nippon Steel Chemical Co., Ltd.); glycidylamine
epoxy resins such as jER630 (available from Mitsubishi Chemical
Corporation), Epiclon 430 (available from DIC Corporation), and
TETRAD-X (available from Mitsubishi Gas Chemical Company, Inc.);
alkyl polyol epoxy resins such as ZX-1542 (available from Nippon
Steel Chemical Co., Ltd.), Epiclon 726 (available from DIC
Corporation), Epolight 80MFA (available from Kyoeisha Chemical Co.,
Ltd.), and Denacol EX-611, (available from Nagase ChemteX
Corporation); rubber-modified epoxy resins such as YR-450, YR-207
(available from Nippon Steel Chemical Co., Ltd.), and Epolead PB
(available from Daicel Corporation); glycidyl esters such as
Denacol EX-147 (available from Nagase ChemteX Corporation);
bisphenol A episulfide resins such as jERYL-7000 (available from
Mitsubishi Chemical Corporation); and other compounds such as
YDC-1312, YSLV-80XY, YSLV-90CR (available from Nippon Steel
Chemical Co., Ltd.), XAC4151 (available from Asahi Kasei
Corporation), jER1031, jER1032 (available from Mitsubishi Chemical
Corporation), EXA-7120 (available from DIC Corporation), and TEPIC
(available from Nissan Chemical Industries, Ltd.).
[0120] The compound containing at least one epoxy group per
molecule has a weight average molecular weight of 300 to 10,000. A
compound having a weight average molecular weight of 300 or more is
preferred since it is unlikely to contaminate the liquid crystal. A
compound having a weight average molecular weight of 10,000 or less
is preferred since it facilitates the control of the sealant
viscosity. The lower limit of the weight average molecular weight
is preferably 500 or more, more preferably 1,000 or more. The upper
limit of the weight average molecular weight is preferably 7,000 or
less, more preferably 5,000 or less, even more preferably 3,000 or
less.
[0121] The curable resin composition containing the compound
containing at least one epoxy group per molecule preferably has a
hydrogen-bonding functional group value of 1.times.10.sup.-4 to
5.times.10.sup.-2 mol/g, more preferably 5.times.10.sup.-4 to
1.times.10.sup.-2 mol/g, even more preferably 1.times.10.sup.-3 to
5.times.10.sup.-3 mol/g. Such a curable resin composition is
preferred since it forms intramolecular hydrogen bonds and thus,
when used as a sealant, does not readily dissolve into the liquid
crystal both before and after curing. This reduces the risk of
contamination of the liquid crystal and thus reduces the problem of
display defects such as white spots, alignment unevenness, and
image-sticking.
[0122] The hydrogen bonds are formed by compounds containing a
hydrogen-bonding functional group or residue. Examples of such
compounds include those containing functional groups such as --OH,
--SH, --NH.sub.2, --NHR (where R is an aromatic or aliphatic
hydrocarbon group or a derivative thereof), --COOH, --CONH.sub.2,
and --NHOH groups and those containing residues such as --NHCO--,
--NH--, --CONHCO--, and --NH--NH-- linkages in the molecule. If the
curable resin composition contains a single compound containing
hydrogen-bonding functional groups, the hydrogen-bonding functional
group value is calculated by the following equation (equation
(1)):
Hydrogen-bonding functional group value (HX) (mol/g)=(number of
hydrogen-bonding functional groups per molecule of Compound
X)/(molecular weight of Compound X) (equation 1)
[0123] If the curable resin composition contains a mixture of
resins containing hydrogen-bonding functional groups, the
hydrogen-bonding functional group value may be calculated by taking
into account the contents per unit weight (weight fractions) of the
individual compounds containing hydrogen-bonding functional groups.
For example, if the compounds containing hydrogen-bonding
functional groups are Compounds A, B, and C, the hydrogen-bonding
functional group value is represented by the following equation
(equation (2)).
Hydrogen-bonding functional group value
(H.sub.ABC)=H.sub.AP.sub.A+H.sub.BP.sub.B+H.sub.CP.sub.C (equation
2)
where P.alpha. is the weight fraction of Compound .alpha..
[0124] A curable resin composition having a hydrogen-bonding
functional group value of less than 1.times.10.sup.-4 mol/g readily
dissolves into the liquid crystal and thus disturbs the alignment
of the liquid crystal. A curable resin composition having a
hydrogen-bonding functional group value of more than
5.times.10.sup.-2 mol/g forms a cured product with high moisture
permeability through which moisture readily enters the liquid
crystal display device.
[0125] The curable resin composition may contain a single compound
containing hydrogen-bonding functional groups that itself has a
hydrogen-bonding functional group value within the above range or
may contain a mixture of compounds containing hydrogen-bonding
functional groups that together have a hydrogen-bonding functional
group value within the above range. That is, the curable resin
composition may contain a single compound or a mixture of compounds
containing hydrogen-bonding functional groups that have an average
hydrogen-bonding functional group value within the above range.
[0126] The curable resin composition containing the compound
containing at least one epoxy group per molecule preferably has a
volume resistivity of 1.times.10.sup.13 .OMEGA.cm or more after
curing. A volume resistivity of less than 1.times.10.sup.13
.OMEGA.cm indicates that the sealant contains ionic impurities. If
such a curable resin composition is used as a sealant, ionic
impurities dissolve into the liquid crystal while a voltage is
being applied. This decreases the voltage holding ratio (VHR) and
increases the ionic density of the liquid crystal layer and causes
display defects such as white spots, alignment unevenness, and
image-sticking.
[0127] The curable resin composition containing the compound
containing at least one epoxy group per molecule preferably has a
resistivity of 1.0.times.10.sup.6 to 1.0.times.10.sup.10 .OMEGA.cm
before curing. A curable resin composition having a resistivity of
less than 1.0.times.10.sup.6 .OMEGA.cm before curing, when used as
a sealant, dissolves into the liquid crystal. This decreases the
voltage holding ratio (VHR) and increases the ionic density of the
liquid crystal layer and causes display defects such as white
spots, alignment unevenness, and image-sticking. A curable resin
composition having a resistivity of more than 1.0.times.10.sup.10
.OMEGA.cm before curing may have poor adhesion to substrates.
[0128] The compound containing at least one epoxy group per
molecule preferably contains at least one ethylenically unsaturated
bond per molecule. Preferred among such compounds are those
containing at least one epoxy group and at least one (meth)acrylic
group per molecule.
[0129] Examples of compounds containing at least one epoxy group
and at least one (meth)acrylic group per molecule include, but not
limited to, (meth)acrylic-modified epoxy resins and
urethane-modified (meth)acrylic epoxy resins.
1) (Meth)Acrylic-Modified Epoxy Resins
[0130] (Meth)acrylic-modified epoxy resins may be prepared by any
method, for example, by reacting (meth)acrylic acid with an epoxy
resin in the presence of a basic catalyst in a usual manner.
[0131] Examples of (meth)acrylic-modified epoxy resins include
partial (meth)acrylates of epoxy resins such as novolac epoxy
resins and bisphenol epoxy resins. Preferred epoxy resins include
biphenyl epoxy resins, naphthalene epoxy resins,
tris(hydroxyphenyl)alkyl epoxy resins, and
tetrakis(hydroxyphenyl)alkyl epoxy resins.
[0132] Specifically, for example, a (meth)acrylic-modified epoxy
resin may be prepared by mixing 360 parts by weight of a resorcinol
epoxy resin (EX-201 available from Nagase ChemteX Corporation), 2
parts by weight of p-methoxyphenol, serving as a polymerization
inhibitor, 2 parts by weight of triethylamine, serving as a
reaction catalyst, and 210 parts by weight of acrylic acid and
reacting the mixture with stirring under reflux at 90.degree. C.
for five hours while supplying air.
[0133] Examples of commercially available (meth)acrylic-modified
epoxy resins include Ebecryl 860, Ebecryl 1561, Ebecryl 3700,
Ebecryl 3600, Ebecryl 3701, Ebecryl 3703, Ebecryl 3200, Ebecryl
3201, Ebecryl 3702, Ebecryl 3412, Ebecryl 860, Ebecryl RDX63182,
Ebecryl 6040, Ebecryl 3800 (available from Daicel-Cytec Co., Ltd.),
EA-1020, EA-1010, EA-5520, EA-5323, EA-CHD, EMA-1020 (available
from Shin Nakamura Chemical Co., Ltd.), Epoxy Ester M-600A, Epoxy
Ester 40EM, Epoxy Ester 70PA, Epoxy Ester 200PA, Epoxy Ester 80MFA,
Epoxy Ester 3002M, Epoxy Ester 3002A, Epoxy Ester 1600A, Epoxy
Ester 3000M, Epoxy Ester 3000A, Epoxy Ester 200EA, Epoxy Ester
400EA (available from Kyoeisha Chemical Co., Ltd.), Denacol
Acrylate DA-141, Denacol Acrylate DA-314, and Denacol Acrylate
DA-911 (available from Nagase ChemteX Corporation).
2) Urethane-Modified (Meth)Acrylic Epoxy Resins
[0134] Urethane-modified (meth)acrylic epoxy resins may be
prepared, for example, by reacting a polyol with a di- or higher
functional isocyanate and then reacting the resulting compound with
a hydroxyl-containing (meth)acrylic monomer and glycidol, by
reacting a di- or higher functional isocyanate with a
hydroxyl-containing (meth)acrylic monomer and glycidol without a
polyol, or by reacting an isocyanate-containing (meth)acrylate with
glycidol. Specifically, for example, a urethane-modified
(meth)acrylic epoxy resin may be prepared by reacting 1 mol of
trimethylolpropane and 3 mol of isophorone diisocyanate in the
presence of a tin-based catalyst and reacting the isocyanate groups
remaining in the resulting compound with hydroxyethyl acrylate,
which is a hydroxyl-containing acrylic monomer, and glycidol, which
is a hydroxyl-containing epoxy compound.
[0135] Examples of polyols include, but not limited to, ethylene
glycol, glycerol, sorbitol, trimethylolpropane, and (poly)propylene
glycol.
[0136] Examples of di- or higher functional isocyanates include,
but not limited to, isophorone diisocyanate, 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, hexamethylene
diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane
4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI,
1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine
diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine
diisocyanate, triphenylmethane triisocyanate,
tris(isocyanatophenyl) thiophosphate, tetramethylxylene
diisocyanate, and 1,6,10-undecane triisocyanate.
[0137] Examples of hydroxyl-containing (meth)acrylic monomers
include, but not limited to, monomers containing one hydroxyl group
in the molecule, including hydroxyethyl (meth)acrylate,
hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate; and
monomers containing two or more hydroxyl groups in the molecule,
including epoxy (meth)acrylates such as bisphenol A-modified epoxy
(meth)acrylate. These may be used alone or in combination.
[0138] The compound containing at least one epoxy group and at
least one (meth)acrylic group per molecule preferably contains a
hydrogen-bonding group, for example, a hydroxyl group and/or a
urethane linkage, to reduce the compatibility with the liquid
crystal and thereby to eliminate contamination. This reduces the
problem of display defects such as white spots, alignment
unevenness, and image-sticking.
[0139] The compound containing at least one epoxy group and at
least one (meth)acrylic group per molecule preferably contains at
least one molecular backbone selected from biphenyl backbones,
naphthalene backbones, bisphenol backbones, and partial
(meth)acrylates of novolac epoxy resins. This improves the heat
resistance of the curable resin composition according to the
present invention.
[0140] The curable resin composition containing the compound
containing at least one epoxy group per molecule may contain a
compound containing an ethylenically unsaturated bond, preferably a
compound containing a (meth)acryloyloxy group. Examples of
compounds containing a (meth)acryloyloxy group include esters
obtained by reacting (meth)acrylic acid with a hydroxyl-containing
compound and urethane (meth)acrylates obtained by reacting an
isocyanate with a hydroxyl-containing (meth)acrylic acid
derivative.
(1) Esters Obtained by Reacting (Meth)Acrylic Acid with
Hydroxyl-Containing Compound
[0141] Examples of monofunctional esters obtained by reacting
(meth)acrylic acid with a hydroxyl-containing compound include, but
not limited to, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxybutyl
(meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate,
isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl
(meth)acrylate, isobornyl (meth)acrylate, cyclohexyl
(meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxyethylene
glycol (meth)acrylate, 2-ethoxyethyl (meth)acrylate,
tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate,
ethylcarbitol (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy
diethylene glycol (meth)acrylate, phenoxy polyethylene glycol
(meth)acrylate, methoxy polyethylene glycol (meth)acrylate,
2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl
(meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, imide
(meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate,
n-butyl (meth)acrylate, propyl (meth)acrylate, n-butyl
(meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, n-octyl (meth)acrylate, isononyl (meth)acrylate,
isomyristyl (meth)acrylate, 2-butoxyethyl (meth)acrylate,
2-phenoxyethyl (meth)acrylate, bicyclopentenyl (meth)acrylate,
isodecyl (meth)acrylate, diethylaminoethyl (meth)acrylate,
dimethylaminoethyl (meth)acrylate, 2-(meth)acryloyloxyethylsuccinic
acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid,
2-(meth)acryloyloxyethyl 2-hydroxypropyl phthalate, glycidyl
(meth)acrylate, and 2-(meth)acryloyloxyethyl phosphate.
[0142] Examples of difunctional esters obtained by reacting
(meth)acrylic acid with a hydroxyl-containing compound include, but
not limited to, 1,4-butanediol di(meth)acrylate, 1,3-butanediol
di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol
di(meth)acrylate, 1,10-decanediol di(meth)acrylate,
2-n-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, dipropylene
glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate,
polypropylene glycol di(meth)acrylate, ethylene glycol
di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene
glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,
propylene oxide adducts of bisphenol A di(meth)acrylate, ethylene
oxide adducts of bisphenol A di(meth)acrylate, ethylene oxide
adducts of bisphenol F di(meth)acrylate,
dimethyloldicyclopentadiene di(meth)acrylate, 1,3-butylene glycol
di(meth)acrylate, neopentyl glycol di(meth)acrylate,
ethylene-oxide-modified isocyanurate di(meth)acrylate,
2-hydroxy-3-acryloyloxypropyl di(meth)acrylate, carbonate diol
di(meth)acrylate, polyether diol di(meth)acrylate, polyester diol
di(meth)acrylate, polycaprolactone diol di(meth)acrylate, and
polybutadiene diol di(meth)acrylate.
[0143] Examples of tri- and higher functional esters obtained by
reacting (meth)acrylic acid with a hydroxyl-containing compound
include, but not limited to, pentaerythritol tri(meth)acrylate,
trimethylolpropane tri(meth)acrylate, propylene oxide adducts of
trimethylolpropane tri(meth)acrylate, ethylene oxide adducts of
trimethylolpropane tri(meth)acrylate, caprolactone-modified
trimethylolpropane tri(meth)acrylate, ethylene oxide adducts of
isocyanurate tri(meth)acrylate, dipentaerythritol
penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate,
ditrimethylolpropane tetra(meth)acrylate, pentaerythritol
tetra(meth)acrylate, glycerol tri(meth)acrylate, propylene oxide
adducts of glycerol tri(meth)acrylate, and
tris(meth)acryloyloxyethyl phosphate.
(2) Urethane (Meth)Acrylates Obtained by Reacting Isocyanate with
Hydroxyl-Containing Acrylic Acid Derivative
[0144] (Meth)acrylates obtained by reacting an isocyanate with a
hydroxyl-containing (meth)acrylic acid derivative may be prepared
by any method, for example, by reacting one equivalent of a
compound containing two isocyanate groups with two equivalents of a
hydroxyl-containing (meth)acrylic acid derivative in the presence
of a tin compound serving as a catalyst.
[0145] Examples of isocyanates that can be used as a raw material
for urethane (meth)acrylates obtained by reacting an isocyanate
with a hydroxyl-containing (meth)acrylic acid derivative include,
but not limited to, isophorone diisocyanate, 2,4-tolylene
diisocyanate, 2,6-tolylene diisocyanate, hexamethylene
diisocyanate, trimethylhexamethylene diisocyanate, diphenylmethane
4,4'-diisocyanate (MDI), hydrogenated MDI, polymeric MDI,
1,5-naphthalene diisocyanate, norbornane diisocyanate, tolidine
diisocyanate, xylylene diisocyanate (XDI), hydrogenated XDI, lysine
diisocyanate, triphenylmethane triisocyanate,
tris(isocyanatophenyl) thiophosphate, tetramethylxylene
diisocyanate, and 1,6,10-undecane triisocyanate.
[0146] Other examples of isocyanates that can be used as a raw
material for urethane (meth)acrylates obtained by reacting an
isocyanate with a hydroxyl-containing (meth)acrylic acid derivative
include chain-extended isocyanates obtained by reacting, with
excess isocyanate, polyols such as ethylene glycol, glycerol,
sorbitol, trimethylolpropane, (poly)propylene glycol, carbonate
diols, polyether diols, polyester diols, and polycaprolactone
diols.
[0147] Examples of hydroxyl-containing (meth)acrylic acid
derivatives include, but not limited to, commercially available
compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxybutyl
(meth)acrylate; mono(meth)acrylates of dihydric alcohols such as
ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol,
1,4-butanediol, and polyethylene glycol; mono(meth)acrylates and
di(meth)acrylates of trihydric alcohols such as trimethylolethane,
trimethylolpropane, and glycerol; and epoxy (meth)acrylates such as
bisphenol A-modified epoxy (meth)acrylates.
[0148] Specifically, for example, a urethane (meth)acrylate may be
prepared by mixing 134 parts by weight of trimethylolpropane, 0.2
part by weight of BHT, serving as a polymerization inhibitor, 0.01
part by weight of dibutyltin dilaurate, serving as a reaction
catalyst, and 666 parts by weight of isophorone diisocyanate,
reacting the mixture with stirring under reflux at 60.degree. C.
for two hours, adding 51 parts by weight of 2-hydroxyethyl
acrylate, and reacting the mixture with stirring under reflux at
90.degree. C. for two hours while supplying air.
[0149] Examples of commercially available urethane (meth)acrylates
include M-1100, M-1200, M-1210, M-1600 (available from Toagosei
Co., Ltd.), Ebecryl 230, Ebecryl 270, Ebecryl 4858, Ebecryl 8402,
Ebecryl 8804, Ebecryl 8803, Ebecryl 8807, Ebecryl 9260, Ebecryl
1290, Ebecryl 5129, Ebecryl 4842, Ebecryl 210, Ebecryl 4827,
Ebecryl 6700, Ebecryl 220, Ebecryl 2220 (available from
Daicel-Cytec Co., Ltd.), Art Resin UN-9000H, Art Resin UN-9000A,
Art Resin UN-7100, Art Resin UN-1255, Art Resin UN-330, Art Resin
UN-3320HB, Art Resin UN-1200TPK, Art Resin SH-500B (available from
Negami Chemical Industrial Co., Ltd.), U-122P, U-108A, U-340P,
U-4HA, U-6HA, U-324A, U-15HA, UA-5201P, UA-W2A, U-1084A, U-6LPA,
U-2HA, U-2PHA, UA-4100, UA-7100, UA-4200, UA-4400, UA-340P, U-3HA,
UA-7200, U-2061BA, U-10H, U-122A, U-340A, U-108, U-6H, UA-4000
(available from Shin Nakamura Chemical Co., Ltd.), AH-600, AT-600,
UA-306H, AI-600, UA-101T, UA-101I, UA-306T, and UA-306I.
[0150] Thermally curable sealants have a problem in that the
viscosity of the resin used as a raw material decreases upon
heating. This results in dissolution of ionic impurities from the
sealant into the liquid crystal in contact with the sealant and
leakage of the liquid crystal due to deformation of the seal
pattern. To reduce the decrease in resin viscosity upon heating, it
is effective to improve the curing rate so that the sealant can be
quickly cured before its viscosity decreases. As discussed above,
it is preferred that the curable resin composition according to the
present invention contain a compound containing an ethylenically
unsaturated bond. More preferably, the curable resin composition
contains a combination of a (meth)acrylic-containing resin, which
can react with radicals, and (2) a thermal radical polymerization
initiator and has a carbon-carbon double bond content of 0.002 to
0.006 mol/g. This allows adjacent carbon-carbon double bonds to
react with each other quickly and thus improves the curing rate of
the resin composition, which results in good leakage
resistance.
[0151] Although a curable resin composition having a carbon-carbon
double bond content of more than 0.006 mol/g has a higher curing
rate, the resulting cured product may have a higher crosslink
density and may thus have a lower adhesion strength with the
substrates that form liquid crystal display panels. A curable resin
composition having a carbon-carbon double bond content of less than
0.002 mol/g has a low curing rate. Thus, a resin composition having
a carbon-carbon double bond content within the above range has a
good balance of curability and adhesion to substrates. A
carbon-carbon double bond content of 0.002 to 0.003 mol/g is
preferred to achieve a better balance of curability and adhesion to
substrates.
[0152] If the curable resin composition contains a mixture of
resins containing carbon-carbon double bonds, the carbon-carbon
double bond content may be calculated by taking into account the
contents per unit weight (weight fractions) of the individual
compounds containing carbon-carbon double bonds. For example, if
the compounds containing carbon-carbon double bonds are Compounds
A, B, and C, the carbon-carbon double bond content is represented
by the following equation (equation (3)):
Carbon-carbon double bond content
(N.sub.ABC)=N.sub.AP.sub.A+N.sub.BP.sub.B+N.sub.CP.sub.C (equation
3)
where N.alpha. is the carbon-carbon double bond content (mol/g) of
Compound .alpha., and P.alpha. is the weight fraction of Compound
.alpha. in Compounds A, B, and C.
[0153] The carbon-carbon double bond content of a curable resin can
be calculated as the number of carbon-carbon double bonds in the
molecule divided by the molecular weight of the resin and is
expressed in mol/g. The molecular weight of each curing resin is
preferably measured by GPC using polystyrene standards. Although
the number average molecular weight and the weight average
molecular weight are calculated in this case, the carbon-carbon
double bond content is preferably calculated from the number
average molecular weight.
[0154] The curable resin composition may contain a single resin
that itself has a carbon-carbon double bond content within the
above range or may contain a mixture of resins that together have a
carbon-carbon double bond content within the above range. That is,
the curable resin composition may contain a single compound or a
mixture of compounds having an average carbon-carbon double bond
within the above range.
[0155] The curable resin composition according to the present
invention may contain a compound containing at least one epoxy
group and at least one (meth)acrylic group per molecule or may
contain a compound containing a (meth)acryloyloxy group. In this
case, the curable resin composition preferably has an
epoxy-to-(meth)acrylic mixing ratio of 15:85 to 95:5, more
preferably 25:75 to 90:10, even more preferably 25:75 to 70:30. A
curable resin composition having a (meth)acrylic equivalent ratio
of less than 30 may have low reactivity and thus, when used as a
sealant, may fail to cure quickly upon heating after coating and
may dissolve considerably into the liquid crystal. A curable resin
composition having a (meth)acrylic equivalent ratio of more than 85
may have insufficient adhesion and moisture resistance. More
preferably, the curable resin composition has an
epoxy-to-(meth)acrylic equivalent ratio of 50:50 to 30:70.
[0156] The curable resin composition containing the compound
containing at least one epoxy group per molecule preferably
contains a thermal curing agent. The thermal curing agent is used
to react and crosslink the epoxy groups and/or ethylenically
unsaturated bonds in the curable resin composition upon heating,
thereby improving the adhesion and moisture resistance of the
curable resin composition after curing.
[0157] Although any thermal curing agent may be used to react epoxy
groups, it is preferred to use a latent thermal curing agent having
a melting point of 100.degree. C. or higher. A thermal curing agent
having a melting point of 100.degree. C. or lower may noticeably
decrease the storage stability.
[0158] If the curable resin composition contains a compound
containing at least one ethylenically unsaturated bond such as a
(meth)acrylic group per molecule, it preferably contains a thermal
radical initiator. The thermal radical initiator is used to react
and crosslink the ethylenically unsaturated bonds in the curable
resin composition upon heating. In particular, the thermal radical
initiator contributes to improving the curing rate and serves to
reduce the permeation of ionic impurities. Although any thermal
radical initiator may be used, it is preferred to use a thermal
radical initiator having a 10-hour half-life temperature of
40.degree. C. to 80.degree. C. A thermal radical initiator having a
10-hour half-life temperature of 40.degree. C. or lower may
noticeably decrease the storage stability.
[0159] Examples of thermal curing agents include dihydrazides such
as 1,3-bis[hydrazinocarbonoethyl-5-isopropylhydantoin](melting
point: 120.degree. C.), adipic acid dihydrazide (melting point:
181.degree. C.), 7,11-octadecadiene-1,18-dicarbohydrazide (melting
point: 160.degree. C.), dodecanedioic acid dihydrazide (melting
point: 190.degree. C.), and sebacic acid dihydrazide (melting
point: 189.degree. C.); dicyandiamides such as dicyandiamide
(melting point: 209.degree. C.); guanidines; imidazoles such as
1-cyanoethyl-2-phenylimidazole,
N-[2-(2-methyl-1-imidazolyl)ethyl]urea,
2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine,
N,N'-bis(2-methyl-1-imidazolylethyl)urea,
N,N'-(2-methyl-1-imidazolylethyl)-adipamide,
2-phenyl-4-methyl-5-hydroxymethylimidazole,
2-phenyl-4,5-dihydroxymethylimidazole, 2-hydroxymethylimidazole
(molecular weight: 98.1, melting point: 115.degree. C.),
2-phenyl-4,5-dihydroxymethylimidazole (molecular weight: 204,
solid, melting point: over 230.degree. C. (degraded)), and
2-methylimidazole (molecular weight: 82, solid, melting point:
137.degree. C. to 145.degree. C.), preferably those containing a
hydroxyl group, which reduces the dissolution of the sealant into
the liquid crystal; acid anhydrides such as modified aliphatic
polyamines, tetrahydrophthalic anhydride, and ethylene glycol
bis(anhydrotrimellitate); and phenol compounds such as adducts of
various amines and epoxy resins, phenol novolac resins, cresol
novolac resins, and xyloc novolac resins. These may be used alone
or in combination.
[0160] If the compound containing at least one (meth)acrylic group
and at least one epoxy group per molecule is an acrylic-modified
epoxy resin, the reactivity of the acrylic epoxy resin varies
greatly depending on the structure. Whereas urethane-modified epoxy
resins have high stability and thus provide good storage stability
when used in combination with highly reactive thermal curing
agents, (Meth)acrylic-modified epoxy resins have high reactivity
and are therefore preferably used in combination with less reactive
thermal curing agents having melting points of 100.degree. C. or
higher.
[0161] The thermal curing agent is preferably added in an amount of
5 to 60 parts by weight, more preferably 10 to 50 parts by weight,
per 100 parts by weight of the curable compound. If the thermal
curing agent is added in an amount outside this range, the
resulting cured product may have low adhesion and chemical
resistance. This may result in an earlier decrease in the
characteristics of the liquid crystal in a high-temperature
high-humidity operation test.
[0162] A preferred thermal curing agent is a coated thermal curing
agent, described below. The coated thermal curing agent according
to the present invention can be used to obtain a one-component
sealant with significantly high storage stability.
[0163] Specifically, the coated thermal curing agent, which is
composed of solid thermal curing agent particles coated with fine
particles that are poorly volatile and poorly soluble in organic
materials, can be used to obtain a sealant containing a curing
agent with high storage stability.
[0164] As used herein, the term "solid thermal curing agent" refers
to a curing agent that is solid at room temperature and that melts
or softens upon heating and starts reacting with a curable resin.
The solid thermal curing agent may be any thermal curing agent
having a melting point or softening point higher than room
temperature. Examples of solid thermal curing agents include solid
amines, phenol compounds, and acid anhydrides. Particularly
preferred are solid amines, which have good reactivity at low
temperature.
[0165] The term "solid amine" refers to a solid compound having one
or more primary to tertiary amino groups in the molecule. Examples
of solid amines include aromatic amines such as m-phenylenediamine
and diaminodiphenylmethane; imidazoles such as 2-methylimidazole,
1,2-dimethylimidazole, and 1-cyanoethyl-2-methylimidazole;
imidazolines such as 2-methylimidazoline; and dihydrazides such as
sebacic acid dihydrazide and isophthalic acid dihydrazide. Examples
of commercially available solid amines include amine adducts and
dicyandiamides such as Amicure PN-23 and Amicure MY-24 (available
from Ajinomoto Fine-Techno Co., Inc.).
[0166] Examples of polyhydric phenol compounds include polyphenols
and novolac phenol resins. Examples of commercially available
polyhydric phenol compounds include jERCURE 170, jERCURE YL6065,
and jERCURE MP402FPI (available from Mitsubishi Chemical
Corporation).
[0167] Examples of acid anhydrides include glycerol
bis(anhydrotrimellitate), ethylene glycol bis(anhydrotrimellitate),
tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
4-methylhexahydrophthalic anhydride, and 3-methyltetrahydrophthalic
anhydride.
[0168] Examples of commercially available acid anhydrides include
jERCURE YH-306 and YH-307 (available from Mitsubishi Chemical
Corporation).
[0169] The solid thermal curing agent particles preferably, but not
necessarily, have an average particle size of 0.1 to 50 .mu.m.
Solid thermal curing agent particles having an average particle
size of less than 0.1 .mu.m may be inefficiently coated with the
fine particles. Solid thermal curing agent particles having an
average particle size of more than 50 .mu.m, when added to a
sealant, may settle during storage and may unevenly cure the resin.
More preferably, the solid thermal curing agent particles have an
average particle size of 0.5 to 10 .mu.m.
[0170] Examples of fine particles for coating the surface of the
solid thermal curing agent particles include oxides, hydroxides,
and halides of silicon, aluminum, titanium, iron, manganese, and
magnesium as well as styrene beads and rubber particles. These fine
particles may be used alone or in combination.
[0171] The fine particles preferably have an average particle size
of 0.05 .mu.m or less. Fine particles having an average particle
size of more than 0.05 .mu.m may inefficiently coat the surface of
the solid thermal curing agent particles. More preferably, the fine
particles have an average particle size of 0.03 .mu.m or less. The
fine particles preferably have a particle size of 10% or less of
that of the solid thermal curing agent particles. Fine particles
having a particle size of 10% or more may be insufficiently
effective in controlling the reactivity.
[0172] The weight ratio of the solid thermal curing agent particles
to the fine particles in the coated thermal curing agent is
preferably 50:1 to 3:1. If the solid thermal curing agent particles
are present in a weight ratio of more than 50, the fine particles
may be insufficiently effective in controlling the reactivity. If
the solid thermal curing agent particles are present in a weight
ratio of less than 3, the fine particles are present in excess and
may thus decrease the curing function. More preferably, the weight
ratio of the solid thermal curing agent particles to the fine
particles is 20:1 to 5:1.
[0173] The surface of the solid thermal curing agent particles may
be coated with the fine particles by any method, for example, by
homogeneously mixing the solid thermal curing agent particles and
the fine particles in a container using a commercially available
blender.
[0174] The coated thermal curing agent is preferably added to the
curable resin composition in an amount of 1 to 100 parts by weight
per 100 parts by weight of the curable resin composition. If the
coated thermal curing agent is added in an amount of less than 1
part by weight, the curable resin composition may be insufficiently
cured. If the coated thermal curing agent is added in an amount of
more than 100 parts by weight, excess residual thermal curing agent
may decrease the properties, such as toughness, of the resulting
cured product.
[0175] The coated thermal curing agent, when added to the curable
resin composition, exhibits high storage stability since the fine
particles on the surface of the solid thermal curing agent
particles minimize the contact between the solid thermal curing
agent and the polymerizable resin during storage at room
temperature. During curing, the solid thermal curing agent
liquefies upon heating and contacts the curable resin without being
blocked by the fine particles, thus quickly initiating a curing
reaction. This improves the storage stability of the curable resin
composition. The coated thermal curing agent can be significantly
easily manufactured at room temperature within a short period of
time without the use of a special reaction.
[0176] The curable resin composition according to the present
invention preferably contains a thermal radical polymerization
initiator. The term "thermal radical polymerization initiator"
refers to a compound that produces radicals when heated, i.e., a
compound that is degraded to produce radical species as it absorbs
thermal energy. The thermal radical polymerization initiator is
preferably present in an amount of 0.01 to 3.0 parts by mass per
100 parts by mass of the resin units. An excessive amount of
thermal radical polymerization initiator results in low viscosity
stability, whereas an insufficient amount of thermal radical
polymerization initiator results in low curability.
[0177] As discussed above, if the curable resin composition
according to the present invention is used as a liquid crystal
sealant, it is preferred to minimize the decrease in the viscosity
of the curable resin composition upon heating since an excessive
decrease in the viscosity of the liquid crystal sealant upon
heating results in dissolution of impurities and leakage of the
liquid crystal. To reduce the decrease in resin viscosity upon
heating, as discussed above, it is advantageous to control the
carbon-carbon double bond content of the curable resin composition
within a predetermined range. This improves the curing rate of the
resin composition and thus promotes gelation. The decrease in resin
viscosity can be further reduced by the proper use of a thermal
radical polymerization initiator.
[0178] The gelation of the curable resin composition is promoted by
the use of a thermal radical polymerization initiator having a low
10-hour half-life temperature. The term "10-hour half-life
temperature" refers to the temperature required for the
concentration of a thermal radical polymerization initiator to
decrease to one half of its initial concentration after a pyrolysis
reaction is performed at constant temperature in the presence of an
inert gas for 10 hours. A curable resin composition containing a
thermal radical polymerization initiator having a low 10-hour
half-life temperature cures readily at low temperatures since
radicals are readily produced at relatively low temperatures. A
curable resin composition containing a thermal radical
polymerization initiator having a high 10-hour half-life
temperature has low curability since radicals are not readily
produced.
[0179] To promote the gelation of the curable resin composition,
therefore, the thermal radical polymerization initiator preferably
has a 10-hour half-life temperature of 40.degree. C. to 80.degree.
C., more preferably 50.degree. C. to 70.degree. C. A thermal
radical polymerization initiator having a 10-hour half-life
temperature of 80.degree. C. or lower, or 70.degree. C. or lower,
readily produces radicals during the curing of the composition (the
curing temperature is typically 80.degree. C. to 150.degree. C.).
This promotes the curing reaction and thus reduces the decrease in
viscosity during thermal curing.
[0180] A thermal radical polymerization initiator having an
extremely low 10-hour half-life temperature, however, induces a
curing reaction even at room temperature. This decreases the
stability of the liquid crystal sealant. A curable resin
composition containing a thermal radical polymerization initiator
having a 10-hour half-life temperature of 40.degree. C. or higher,
preferably 50.degree. C. or higher, exhibits good stability during
storage and the application of the sealant to substrates (which is
typically performed at room temperature).
[0181] Specifically, the 10-hour half-life temperature of the
thermal radical polymerization initiator is determined as
follows.
[0182] Assuming that the pyrolysis reaction is a first-order
reaction gives the following equation.
ln(C.sub.0/C.sub.t)=kd.times.t [Math. 1]
where
[0183] C.sub.0: initial concentration of thermal radical
polymerization initiator
[0184] C.sub.t: concentration of thermal radical polymerization
initiator after t hours
[0185] kd: rate constant of pyrolysis
[0186] t: reaction time
[0187] The half-life is the time required for the concentration of
a thermal radical polymerization initiator to decrease to one-half
of its initial concentration, i.e., the time at which
C.sub.t-C.sub.0/2. Hence, assuming that the thermal radical
polymerization initiator has a half-life of t hours gives the
following equation.
kd=(1/t)ln 2 [Math. 2]
[0188] Substituting the Arrhenius equation, which describes the
temperature dependence of the rate constant, gives the following
equation.
kd=Aexp (-.DELTA.E/RT)
(1/t)ln 2:=Aexp(-.DELTA.E/RT) [Math. 3]
where
[0189] A: frequency factor
[0190] .DELTA.E: activation energy
[0191] R: gas constant (8.314 J/molK)
[0192] T: absolute temperature (K)
[0193] The values of A and .DELTA.E are disclosed in J. Brandrup et
al., "Polymer Handbook, 4th Edition, Volume 1, pages II-2 to 11-69,
John & Wiley (1999)". Hence, substituting t=10 hours give the
10-hour half-life temperature T.
[0194] Preferred thermal radical polymerization initiators include
organic peroxides and azo compounds. Examples of organic peroxides
include ketone peroxides, peroxyketals, hydroperoxides, dialkyl
peroxides, peroxyesters, diacyl peroxides, and
peroxydicarbonates.
[0195] Specific examples are shown below, where the numbers in
parentheses beside the individual compounds are their respective
10-hour half-life temperatures (see catalogues available from Wako
Pure Chemical Industries, Ltd. and API Corporation and the polymer
handbook shown above).
[0196] Examples of ketone peroxides include methyl ethyl ketone
peroxide (109.degree. C.) and cyclohexanone peroxide (100.degree.
C.).
[0197] Examples of peroxyketals include
1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane (87.degree. C.),
1,1-bis(t-hexylperoxy)cyclohexane (87.degree. C.),
1,1-bis(t-butylperoxy)cyclohexane (91.degree. C.),
2,2-bis(t-butylperoxy)butane (103.degree. C.),
1,1-(t-amylperoxy)cyclohexane (93.degree. C.), n-butyl
4,4-bis(t-butylperoxy)valerate (105.degree. C.), and
2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane (95.degree. C.).
[0198] Examples of hydroperoxides include P-methane hydroperoxide
(128.degree. C.), diisopropylbenzene peroxide (145.degree. C.),
1,1,3,3-tetramethylbutyl hydroperoxide (153.degree. C.), cumene
hydroperoxide (156.degree. C.), and t-butyl hydroperoxide
(167.degree. C.).
[0199] Examples of dialkyl peroxides include
.alpha.,.alpha.-bis(t-butylperoxy)diisopropylbenzene (119.degree.
C.), dicumyl peroxide (116.degree. C.),
2,5-dimethyl-2,5-bis(t-butylperoxy)hexane (118.degree. C.), t-butyl
cumyl peroxide (120.degree. C.), t-amyl peroxide (123.degree. C.),
di-t-butyl peroxide (124.degree. C.), and
2,5-dimethyl-2,5-bis(t-butylperoxy)hexane-3 (129.degree. C.).
[0200] Examples of peroxyesters include cumyl peroxyneodecanoate
(37.degree. C.), 1,1,3,3-tetramethylbutyl peroxyneodecanoate
(41.degree. C.), t-hexyl peroxyneodecanoate (45.degree. C.),
t-butyl peroxyneodecanoate (46.degree. C.), t-amyl
peroxyneodecanoate (46.degree. C.), t-hexyl peroxypivalate
(53.degree. C.), t-butyl peroxypivalate (55.degree. C.), t-amyl
peroxypivalate (55.degree. C.), 1,1,3,3-tetramethylbutyl
peroxy-2-ethylhexanoate (65.degree. C.),
2,5-dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane (66.degree. C.),
t-hexyl peroxy-2-ethylhexanoate (70.degree. C.), t-butyl
peroxy-2-ethylhexanoate (72.degree. C.), t-amyl
peroxy-2-ethylhexanoate (75.degree. C.), t-butyl peroxyisobutyrate
(82.degree. C.), t-hexylperoxyisopropyl monocarbonate (95.degree.
C.), t-butylperoxymaleic acid (96.degree. C.), t-amyl
peroxy-n-octoate (96.degree. C.), t-amyl peroxyisononanoate
(96.degree. C.), t-butyl peroxy-3,5,5-trimethylhexanoate
(97.degree. C.), t-butyl peroxylaurate (98.degree. C.),
t-butylperoxyisopropyl monocarbonate (99.degree. C.),
t-butylperoxy-2-ethylhexyl monocarbonate (99.degree. C.), t-hexyl
peroxybenzoate (99.degree. C.),
2,5-dimethyl-2,5-bis(benzoylperoxy)hexane (100.degree. C.), t-amyl
peroxyacetate (100.degree. C.), t-amyl peroxybenzoate (100.degree.
C.), t-butyl peroxyacetate (102.degree. C.), and t-butyl
peroxybenzoate (104.degree. C.).
[0201] Examples of diacyl peroxides include diisobutyryl peroxide
(33.degree. C.), di-3,5,5-trimethylhexanoyl peroxide (60.degree.
C.), dilauroyl peroxide (62.degree. C.), disuccinoyl peroxide
(66.degree. C.), and dibenzoyl peroxide (73.degree. C.).
[0202] Examples of peroxydicarbonates include di-n-propyl
peroxydicarbonate (40.degree. C.), diisopropyl peroxydicarbonate
(41.degree. C.), bis(4-t-butylcyclohexyl) peroxydicarbonate
(41.degree. C.), di-2-ethylhexyl peroxydicarbonate (44.degree. C.),
t-amyl peroxypropyl carbonate (96.degree. C.), and t-amyl
peroxy-2-ethylhexyl carbonate (99.degree. C.).
[0203] The curable resin composition containing the compound
containing at least one epoxy group per molecule may contain a
radical polymerization inhibitor.
[0204] Examples of radical polymerization inhibitors include
2,6-di-t-butylcresol, butylated hydroxyanisole,
2,6-di-t-butyl-4-ethylphenol, stearyl
0-(3,5-di-t-butyl-4-hydroxyphenyl)propionate,
2,2'-methylenebis(4-methyl-6-t-butylphenol),
2,2'-methylenebis(4-ethyl-6-t-butylphenol),
4,4'-thiobis(3-methyl-6-t-butylphenol),
4,4-butylidenebis(3-methyl-6-t-butylphenol),
3,9-bis[1,1-dimethyl-2-[.beta.-(3-t-butyl-4-hydroxy-5-methylphenyl)propio-
nyloxy]ethyl], 2,4,8,10-tetraoxaspiro[5,5]undecane,
tetrakis[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)
propionate]methane,
1,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-sec-triazine-2,4,6-(1H,3H,5-
H)trione, hydroquinone, p-methoxyphenol, p-benzoquinone,
toluquinone, t-butyl-p-benzoquinone, 2,5-di-t-butyl-p-benzoquinone,
and 2,5-diphenyl-p-benzoquinone, preferably p-benzoquinone,
toluquinone, and t-butyl-p-benzoquinone. These radical
polymerization inhibitors may be used alone or in combination.
[0205] The radical polymerization inhibitor is preferably added in
an amount of 0.1 to 0.4 part by weight per 100 parts by weight of
the curable resin composition. If the radical polymerization
inhibitor is added in an amount of less than 0.1 part by weight,
the curable resin composition may accidentally undergo a curing
reaction in the event of unintentional heating during the storage
of the sealant or during the manufacture of the liquid crystal
display device. This induces changes in properties such as
increased thickness. If the radical polymerization inhibitor is
added in an amount of more than 0.4 part by weight, the resulting
sealant may exhibit noticeably low thermal curability and may thus
fail to cure when heated to cure the sealant.
[0206] The curable resin composition containing the compound
containing at least one epoxy group per molecule may further
contain a silane coupling agent. The silane coupling agent serves
mainly as an adhesion aid to improve the adhesion between the
sealant and the liquid crystal display substrate. The silane
coupling agent may also be used to treat the surface of an
inorganic or organic filler that is added, for example, to improve
the adhesion through a stress dispersion effect or to improve the
linear expansion coefficient. This improves the interaction between
the filler and the resins that form the sealant.
[0207] The silane coupling agent is preferably a silane containing
at least one functional group selected from Group (2-A) and at
least one functional group selected from Group (2-B) below.
##STR00020##
[0208] Specific examples of such silanes include
.gamma.-aminopropyltrimethoxysilane,
.gamma.-mercaptopropyltrimethoxysilane,
.gamma.-glycidoxypropyltrimethoxysilane, and
.gamma.-isocyanatopropyltrimethoxysilane. These silanes may be used
alone or in combination.
[0209] A silane having such a structure, when used as a silane
coupling agent, improves the adhesion to substrates and also
reduces the dissolution of the curable resin into the liquid
crystal by combining chemically with the curable resin through the
functional group from Group (2-B).
[0210] To treat the surface of the filler with the silane coupling
agent, the silane is mixed with the curable resin components, and
the mixture is heated. Upon heating, the silane combines chemically
with the curable resin components via the functional group from
Group (2-B). To improve the reaction efficiency, it is preferred to
stir the resin mixture during heating. The resin mixture may be
stirred by any method, typically by rotating a stirrer or stirring
impeller with a motor. The preferred heating temperature is
30.degree. C. to 70.degree. C. A heating temperature of lower than
30.degree. C. may result in insufficient reaction between the
silane and the curable resins. A heating temperature of higher than
70.degree. C. may trigger thermal curing. A more preferred heating
temperature is 40.degree. C. to 60.degree. C. The preferred heating
time is one to two hours. A heating time of less than one hour may
be insufficient to react all functional groups in the silane and
may thus leave unreacted silane.
[0211] After heating, 10% or less of the at least one functional
group selected from Group (2-B) should remain. If more than 10% of
the at least one functional group selected from Group (2-B)
remains, it may react with and thicken the resin components during
storage and may dissolve into and contaminate the liquid crystal.
The amount of at least one functional group selected from Group
(2-B) remaining may be determined by 1H-NMR from the ratio of the
peak intensity of the functional group in the silane to the peak
intensity after heating.
[0212] A filler may be added to the curable resin composition
containing the compound containing at least one epoxy group per
molecule to control the viscosity and to improve the adhesion
through a stress dispersion effect.
[0213] Examples of fillers include, but not limited to, inorganic
fillers such as talc, asbestos, silica, diatomite, smectite,
bentonite, calcium carbonate, magnesium carbonate, alumina,
montmorillonite, diatomite, zinc oxide, iron oxide, magnesium
oxide, tin oxide, titanium oxide, magnesium hydroxide, aluminum
hydroxide, glass beads, silicon nitride, barium sulfate, gypsum,
calcium silicate, sericite, activated clay, and aluminum nitride;
and organic fillers such as polyester particles, polyurethane
particles, vinyl polymer particles, acrylic polymer particles, and
rubber particles.
[0214] These fillers may have any shape, including regular shapes
such as spheres, needles, and plates and irregular shapes.
[0215] The curable resin composition containing the compound
containing at least one epoxy group per molecule may contain resin
particles.
[0216] The resin particles include a core particle made of a resin
having rubber elasticity and a glass transition temperature of
-10.degree. C. or lower and a shell layer formed on the surface of
the core particle and made of a resin having a glass transition
temperature of 50.degree. C. to 150.degree. C.
[0217] Unless otherwise specified, the term "glass transition
temperature" as used herein refers to the temperature measured by
normal DSC at a heating rate of 10.degree. C./min.
[0218] Examples of resins having rubber elasticity and a glass
transition temperature of -10.degree. C. or lower include, but not
limited to, polymers of (meth)acrylic monomers.
[0219] Examples of (meth)acrylic monomers include ethyl acrylate,
propyl acrylate, n-butyl acrylate, cyclohexyl acrylate,
2-ethylhexyl acrylate, ethyl methacrylate, and butyl methacrylate.
These (meth)acrylic monomers may be homopolymerized or
copolymerized.
[0220] Examples of resins having a glass transition temperature of
50.degree. C. to 150.degree. C. include, but not limited to,
polymers of isopropyl methacrylate, t-butyl methacrylate,
cyclohexyl methacrylate, phenyl methacrylate, methyl methacrylate,
styrene, 4-chlorostyrene, 2-ethylstyrene, acrylonitrile, and vinyl
chloride. These monomers may be used alone or in combination.
[0221] Although the particle size of the resin particles may be
selected depending on the purpose of use, it is preferably 0.01 to
5 .mu.m. Resin particles having a particle size within this range
have a sufficient surface area with the photocurable resin to cause
the core layer to swell effectively. When used in a sealant for
liquid crystal displays, such resin particles also facilitate the
procedure of defining the gap between substrates.
[0222] The resin particles may be manufactured by any method, for
example, by forming core particles through emulsion polymerization
using the monomer for the core alone and then adding and
polymerizing the monomer for the shell to form a shell layer on the
surface of the core particles.
[0223] The resin particles are preferably added to the curable
resin composition in an amount of 15 to 50 parts by weight per 100
parts by weight of the photocurable resin. If the resin particles
are added in an amount of less than 15 parts by weight, they may be
insufficiently effective in improving the adhesion. If the resin
particles are added in an amount of more than 50 parts by weight,
they may thicken the curable resin composition more than necessary.
More preferably, the resin particles are added in an amount of 20
parts by weight or less.
[0224] The curable resin composition containing the compound
containing at least one epoxy group per molecule is cured with
heat. Preferably, the curable resin composition is cured only with
heat.
Alignment Layer
[0225] The liquid crystal display device according to the present
invention may include alignment layers for aligning the liquid
crystal composition on the surfaces of the first and second
substrates adjacent to the liquid crystal composition.
[0226] Examples of alignment layer materials that can be used
include transparent organic materials such as polyimides,
polyamides, benzocyclobutene (BCB) polymers, and polyvinyl alcohol.
Particularly preferred are polyimide alignment layers, which are
formed by the imidation of polyamic acids synthesized from diamines
such as aliphatic and alicyclic diamines, including
p-phenylenediamine and 4,4'-diaminodiphenylmethane, and aliphatic
and alicyclic tetracarboxylic anhydrides such as
butanetetracarboxylic anhydride and
2,3,5-tricarboxycyclopentylacetic anhydride or aromatic
tetracarboxylic anhydrides such as pyromellitic dianhydride.
Although rubbing is a typical alignment process, photoalignment by
photodegradation may instead be used in this case. Alternatively,
polyimide alignment layers may be used without an alignment
process, for example, if they are used as vertical alignment
layers.
[0227] Other alignment layer materials include compounds containing
functional groups such as chalcone, cinnamate, cinnamoyl, and azo
groups. These alignment layer materials may be used in combination
with other materials such as polyimides and polyamides. In this
case, either rubbing or photoalignment may be used.
[0228] Although the alignment layers are typically formed by
applying the alignment layer material to the substrates using a
process such as spin coating to form a resin layer, other processes
such as uniaxial drawing and the Langmuir-Blodgett technique may be
used instead.
Transparent Electrode
[0229] The liquid crystal display device according to the present
invention may include transparent electrodes made of conductive
metal oxides. Examples of metal oxides that can be used include
indium oxide (In.sub.2O.sub.3), tin oxide (SnO.sub.2), zinc oxide
(ZnO), indium tin oxide (In.sub.2O.sub.3--SnO.sub.2), indium zinc
oxide (In.sub.2O.sub.3--ZnO), niobium-doped titanium dioxide
(Ti.sub.1-xNb.sub.xO.sub.2), fluorine-doped tin oxide, graphene
nanoribbons, and metal nanowires, preferably zinc oxide (ZnO),
indium tin oxide (In.sub.2O.sub.3--SnO.sub.2), and indium zinc
oxide (In.sub.2O.sub.3--ZnO). These transparent conductive films
may be patterned by techniques such as photoetching and mask
patterning.
[0230] The liquid crystal display device according to the present
invention is particularly useful as an active-matrix-driven liquid
crystal display device and can be used as a VA, PSVA, PSA, IPS,
FFS, or ECB liquid crystal display device.
[0231] This liquid crystal display device can be used in
combination with backlights for various applications, including
liquid crystal display televisions, personal computer monitors,
cell phone and smartphone displays, notebook personal computers,
portable information terminals, and digital signage. Examples of
backlights include cold cathode fluorescent lamp backlights and
pseudo-white backlights with two or three wavelength peaks that
include inorganic light-emitting diodes or organic EL devices.
EXAMPLES
[0232] The present invention is further illustrated by the
following examples, although these examples are not intended to
limit the invention. In the following Examples and Comparative
Examples, percentages for compositions are by mass.
[0233] The properties measured in the examples are as follows:
[0234] T.sub.ni: nematic-isotropic liquid phase transition
temperature (.degree. C.)
[0235] .DELTA.n: refractive index anisotropy at 25.degree. C.
[0236] .DELTA..di-elect cons.: dielectric anisotropy at 25.degree.
C.
[0237] .eta.: viscosity (mPas) at 20.degree. C.
[0238] .gamma.1: rotational viscosity (mPas) at 25.degree. C.
[0239] VHR: voltage holding ratio (%) at 70.degree. C. (as
determined by applying a voltage of 5 V to a cell having a cell
thickness of 3.5 .mu.m and filled with a liquid crystal composition
for a pulse duration of 64 .mu.s, measuring the voltage after a
frame time of 200 ms, and calculating the percentage of the
measured voltage to the initial applied voltage)
Alignment Unevenness
[0240] Each liquid crystal display device was visually inspected
for alignment unevenness around the contact area between the
sealant and the liquid crystal with and without a voltage being
applied. The liquid crystal display device was rated on the
following four-level scale:
[0241] A: no alignment unevenness
[0242] B: slight and acceptable alignment unevenness
[0243] C: unacceptable alignment unevenness
[0244] D: severe alignment unevenness
Image-Sticking
[0245] Each liquid crystal display device was evaluated for
image-sticking as follows. After a predetermined fixed pattern was
displayed within the display area for 1,000 hours, a uniform image
was displayed over the entire screen and was visually inspected for
image-sticking of the fixed pattern. The liquid crystal display
device was rated on the following four-level scale:
[0246] A: no image-sticking
[0247] B: slight and acceptable image-sticking
[0248] C: unacceptable image-sticking
[0249] D: severe image-sticking
Volume Resistivity of Sealant after Curing
[0250] Each sealant was thinly and uniformly applied to the
chromium-coated surface of a chromium-coated glass substrate and
was cured with UV radiation to form a UV-cured coating having a
size of 85 mm.times.85 mm and a thickness of 3 m. Another
chromium-coated glass substrate was placed on the UV-cured coating
with the chromium-coated surface thereof facing the UV-cured
coating. These substrates were heated and pressed under a load on a
hot plate at 120.degree. C. for one hour to obtain a test sample.
The area (S (cm.sup.2)) of the sealant on the test sample was
measured. A predetermined voltage (V (V)) was applied between the
chromium-coated surfaces of the opposing chromium-coated glass
substrates using a constant-voltage generator (PA36-2A regulated DC
power supply available from Kenwood Corporation). The current (A
(A)) flowing through the coating was measured using an ammeter
(R644C digital multimeter available from Advantest Corporation).
The volume resistivity (Qcm) was calculated by the following
equation:
Volume resistivity (.OMEGA.cm)=(VS)/(AT)
where T (cm) is the thickness of the sealant. A DC voltage of 500 V
was applied for one minute.
Resistivity of Sealant Before Curing
[0251] The resistivity of each sealant before curing was measured
under standard temperature and humidity conditions (20.degree. C.,
65% RH) using a resistivity meter (SR-6517 available from Toyo
Corporation) and electrodes for liquids (LE-21 available from Ando
Electric Co., Ltd.).
[0252] The compounds used in the examples are represented by the
following abbreviations:
Side Chains and Linking Groups
[0253] -n: --C.sub.nH.sub.2n+1 linear alkyl group of n carbon
atoms
[0254] n-: C.sub.nH.sub.2n+1-linear alkyl group of n carbon
atoms
[0255] --On: --OC.sub.nH.sub.2n+1 linear alkoxy group of n carbon
atoms
[0256] nO--: C.sub.nH.sub.2n+1O-- linear alkoxy group of n carbon
atoms
[0257] --V: --CH--CH.sub.2
[0258] V--: CH.sub.2--CH--
[0259] --V1: --CH.dbd.CH--CH.sub.3
[0260] 1V--: CH.sub.3--CH.dbd.CH--
[0261] -2V: --CH.sub.2--CH.sub.2--CH.dbd.CH.sub.3
[0262] V2-: CH.sub.3.dbd.CH--CH.sub.2--CH.sub.2--
[0263] -2V1: --CH.sub.2--CH.sub.2--CH.dbd.CH--CH.sub.3
[0264] 1V2-: CH.sub.3--CH.dbd.CH--CH.sub.2--CH.sub.2
[0265] -1O--: --CH.sub.2O--
[0266] --O1-: --OCH.sub.2--
Cyclic Structures
##STR00021##
[0267] Preparation of Curable Resin Composition
Synthesis Example A
Synthesis of Modified Epoxy Resin (A)
[0268] A solvent was heated to the reflux temperature with nitrogen
purging. To the solvent was added dropwise over five hours a
solution containing 100 parts by weight of glycidyl methacrylate,
40 parts by weight of methyl methacrylate, 20 parts by weight of
hydroxyethyl methacrylate, 40 parts by weight of styrene, 200 parts
by weight of n-butyl methacrylate, and 40 parts by weight of a
polymerization initiator (Perbutyl O available from NOF
Corporation, 10-hour half-life temperature: 72.1.degree. C.,
t-butyl peroxy-2-ethylhexanoate). The solution was maintained at
100.degree. C. for additional five hours. A hundred parts by weight
of the resulting resin was filtered through a column filled with 30
parts by weight of a natural combination of quartz and kaolin
(Sillitin V 85 available from Hoffmann Mineral GmbH) to allow it to
adsorb ionic impurities from the reaction product. The solvent was
removed to obtain Modified Epoxy Resin (A), which contained
glycidyl and hydroxyl groups.
[0269] Modified Epoxy Resin (A) had a weight average molecular
weight Mw of 4,020 (as measured by GPC), an epoxy equivalent weight
of 640 g/eq, and a hydrogen-bonding functional group value of
3.4.times.10.sup.4 mol/g.
Synthesis Example B
Synthesis of Acrylic-Modified Epoxy Resin (B)
[0270] A solution was prepared by uniformly dissolving, in a
solvent, 100 parts by weight of a bisphenol F epoxy resin
(YDF-8170C available from Nippon Steel Chemical Co., Ltd.), 22.5
parts by weight of acrylic acid, and 0.125 parts by weight of
triethanolamine. The solution was stirred under reflux at
110.degree. C. for five hours. A hundred parts by weight of the
resulting resin was filtered through a column filled with 30 parts
by weight of a natural combination of quartz and kaolin (Sillitin V
85 available from Hoffmann Mineral GmbH) to allow it to adsorb
ionic impurities from the reaction product. The solvent was removed
to obtain Acrylic-Modified Epoxy Resin (B).
[0271] Acrylic-Modified Epoxy Resin (B) had a weight average
molecular weight Mw of 392 (as measured by GPC), a hydrogen-bonding
functional group value of 2.6.times.10.sup.-3 mol/g, and a
carbon-carbon double bond content of 2.6.times.10.sup.-3 mol/g.
Synthesis Example C
Synthesis of Monoacrylate-Modified Epoxy Resin (C)
[0272] A solution was prepared by uniformly dissolving, in a
solvent, 100 parts by weight of a bisphenol F epoxy resin
(YDF-8170C available from Nippon Steel Chemical Co., Ltd.), 22.5
parts by weight of acrylic acid, and 0.125 part by weight of
triethanolamine. The solution was stirred under reflux at
110.degree. C. for five hours. A hundred parts by weight of the
resulting resin was filtered through a column filled with 30 parts
by weight of a natural combination of quartz and kaolin (Sillitin V
85 available from Hoffmann Mineral GmbH) to allow it to adsorb
ionic impurities from the reaction product. The solvent was removed
to obtain Monoacrylate-Modified Epoxy Resin (C).
[0273] Monoacrylate-Modified Epoxy Resin (C) had a weight average
molecular weight Mw of 398 (as measured by GPC), a hydrogen-bonding
functional group value of 2.5.times.10.sup.-3 mol/g, and a
carbon-carbon double bond content of 2.5.times.10.sup.-3 mol/g.
Synthesis Example D
Synthesis of Diacrylate-Modified Epoxy Resin (D)
[0274] A solution was prepared by uniformly dissolving, in a
solvent, 100 parts by weight of a bisphenol F epoxy resin
(YDF-8170C available from Nippon Steel Chemical Co., Ltd.), 45
parts by weight of acrylic acid, and 0.20 part by weight of
triethanolamine. The solution was stirred under reflux at
110.degree. C. for five hours. A hundred parts by weight of the
resulting resin was filtered through a column filled with 30 parts
by weight of a natural combination of quartz and kaolin (Sillitin V
85 available from Hoffmann Mineral GmbH) to allow it to adsorb
ionic impurities from the reaction product. The solvent was removed
to obtain Diacrylate-Modified Epoxy Resin (D).
[0275] Diacrylate-Modified Epoxy Resin (D) had a weight average
molecular weight Mw of 484 (as measured by GPC), a hydrogen-bonding
functional group value of 4.3.times.10.sup.-3 mol/g, and a
carbon-carbon double bond content of 4.3.times.10.sup.-3 mol/g.
Synthesis Example E
Synthesis of Diacrylate-Modified Epoxy Resin (E)
[0276] A solution was prepared by uniformly dissolving, in a
solvent, 117 parts by weight of resorcinol diglycidyl ether
(Denacol EX-201 available from Nagase ChemteX Corporation, epoxy
equivalent weight: 117 eq/g), 79 parts by weight of acrylic acid,
and 1 part by weight of t-butylammonium bromide. The solution was
stirred at 90.degree. C. for two hours and was then stirred under
reflux for six hours to perform the reaction. The reaction solution
was washed with ultrapure water, and the solvent was removed. A
hundred parts by weight of the resulting resin was filtered through
a column filled with 30 parts by weight of a natural combination of
quartz and kaolin (Sillitin V 85 available from Hoffmann Mineral
GmbH) to allow it to adsorb ionic impurities from the reaction
product. The solvent was removed to obtain Diacrylate-Modified
Epoxy Resin (E).
[0277] Diacrylate-Modified Epoxy Resin (E) had a weight average
molecular weight Mw of 366 (as measured by GPC), a hydrogen-bonding
functional group value of 5.3.times.10.sup.-3 mol/g, and a
carbon-carbon double bond content of 5.3.times.10.sup.-3 mol/g.
Synthesis Example F
Synthesis of Diacrylate-Modified Epoxy Resin (F)
[0278] A solution was prepared by uniformly dissolving, in a
solvent, 100 parts by weight of a diphenyl ether epoxy resin
(YSLV-80DE available from Nippon Steel Chemical Co., Ltd., melting
point: 84.degree. C.), 0.2 part by weight of a polymerization
inhibitor (p-methoxyphenol), 0.2 part by weight of a reaction
catalyst (triethylamine), and 40 parts by weight of acrylic acid.
While air was supplied, the solution was stirred at 80.degree. C.
for two hours and was then stirred under reflux for 36 hours to
perform the reaction. The reaction solution was washed with
ultrapure water, and the solvent was removed. A hundred parts by
weight of the resulting resin was filtered through a column filled
with 30 parts by weight of a natural combination of quartz and
kaolin (Sillitin V 85 available from Hoffmann Mineral GmbH) to
allow it to adsorb ionic impurities from the reaction product. The
solvent was removed to obtain Diacrylate-Modified Epoxy Resin
(F).
[0279] Diacrylate-Modified Epoxy Resin (F) had a weight average
molecular weight Mw of 459 (as measured by GPC), a hydrogen-bonding
functional group value of 3.7.times.10.sup.-3 mol/g, and a
carbon-carbon double bond content of 3.7.times.10.sup.3 mol/g.
Synthesis Example G
Synthesis of Diacrylate-Modified Epoxy Resin (G)
[0280] A solution was prepared by uniformly dissolving, in a
solvent, 296.2 g (2 mol) of phthalic anhydride, 917.0 g (2 mol) of
an adduct of 2-hydroxyethyl acrylate and 6-hexanolide (Placcel FA3
available from Daicel Corporation, molecular weight: 459 g/mol), 4
g of triethylamine, and 0.9 g of hydroquinone. The solution was
stirred at 110.degree. C. to perform the reaction. The reaction
temperature was adjusted to 90.degree. C. when the acid value of
the reaction mixture reached 96 mg KOH/g. To the reaction mixture
were added 680.82 g (2 mol) of bisphenol A diglycidyl ether and 1.6
g of tetrabutylammonium bromide. The reaction was performed at
90.degree. C. until the acid value of the reaction mixture reached
2 mg KOH/g.
[0281] To the reaction mixture were added 144.1 g (2 mol) of
acrylic acid and 1.8 g of hydroquinone. The mixture was reacted at
80.degree. C. for two hours while air was supplied to the flask.
The temperature was increased to 90.degree. C., and the reaction
was continued. The reaction was performed until the acid value of
the reaction mixture reached 2 mg KOH/g. After the reaction was
complete, the reaction mixture was washed with ultrapure water, and
the solvent was removed. A hundred parts by weight of the resulting
resin was filtered through a column filled with 30 parts by weight
of a natural combination of quartz and kaolin (Sillitin V 85
available from Hoffmann Mineral GmbH) to allow it to adsorb ionic
impurities from the reaction product. The solvent was removed to
obtain Diacrylate-Modified Epoxy Resin (G).
[0282] Diacrylate-Modified Epoxy Resin (G) had a weight average
molecular weight Mw of 1,005 (as measured by GPC), a
hydrogen-bonding functional group value of 1.9.times.10.sup.-3
mol/g, and a carbon-carbon double bond content of
1.9.times.10.sup.-3 mol/g.
Synthesis Example H
Synthesis of Partially Acrylic-Modified Epoxy Resin (H)
[0283] A solution was prepared by uniformly dissolving, in a
solvent, 100 parts by weight of a diphenyl ether epoxy resin
(YSLV-80DE available from Nippon Steel Chemical Co., Ltd., melting
point: 84.degree. C.), 0.2 part by weight of a polymerization
inhibitor (p-methoxyphenol), 20 parts by weight of acrylic acid,
and 0.2 part by weight of a reaction catalyst (triethylamine).
While air was supplied, the solution was stirred at 80.degree. C.
for two hours and was then stirred under reflux for 24 hours to
perform the reaction. After the reaction was complete, the reaction
mixture was purified through a column and was washed with ultrapure
water, and the solvent was removed. A hundred parts by weight of
the resulting resin was filtered through a column filled with 30
parts by weight of a natural combination of quartz and kaolin
(Sillitin V 85 available from Hoffmann Mineral GmbH) to allow it to
adsorb ionic impurities from the reaction product. The solvent was
removed to obtain Partially Acrylic-Modified Epoxy Resin (H), in
which 50% of the epoxy groups were acrylated.
[0284] Partially Acrylic-Modified Epoxy Resin (H) had a weight
average molecular weight Mw of 386 (as measured by GPC), a
hydrogen-bonding functional group value of 2.2.times.10.sup.-3
mol/g, and a carbon-carbon double bond content of
2.2.times.10.sup.3 mol/g.
Synthesis Example I
Synthesis of Partially Methacrylic-Modified Epoxy Resin (I)
[0285] A solution was prepared by uniformly dissolving, in a
solvent, 163 parts by weight of a bisphenol E epoxy resin (R-1710
available from Printec Corporation). To the solution were added 0.5
part by weight of p-methoxyphenol, serving as a polymerization
inhibitor, 0.5 part by weight of triethylamine, serving as a
reaction catalyst, and 40 parts by weight of methacrylic acid.
While air was supplied, the mixture was stirred under reflux at
90.degree. C. for five hours to perform the reaction.
[0286] After the reaction was complete, the reaction mixture was
purified through a column and was washed with ultrapure water, and
the solvent was removed. A hundred parts by weight of the resulting
resin was filtered through a column filled with 30 parts by weight
of a natural combination of quartz and kaolin (Sillitin V 85
available from Hoffmann Mineral GmbH) to allow it to adsorb ionic
impurities from the reaction product. The solvent was removed to
obtain Partially Methacrylic-Modified Epoxy Resin (I), in which 50%
of the epoxy groups were methacrylated.
[0287] Partially Methacrylic-Modified Epoxy Resin (I) had a weight
average molecular weight Mw of 436 (as measured by GPC), a
hydrogen-bonding functional group value of 4.6.times.10.sup.-3
mol/g, and a carbon-carbon double bond content of
2.3.times.10.sup.-3 mol/g.
Synthesis Example J
Synthesis of Urethane-Modified Methacrylic Epoxy Resin (J)
[0288] A mixture was prepared from 1,100 parts by weight of
trimethylolpropane, 1.6 parts by weight of
3,5-dibutyl-4-hydroxytoluene, serving as a polymerization
inhibitor, 0.08 part by weight of dibutyltin dilaurate, serving as
a reaction catalyst, and 6,080 parts by weight of diphenylmethane
diisocyanate. The mixture was stirred under reflux at 60.degree. C.
for two hours to perform the reaction. To the mixture were added
235 parts by weight of 2-hydroxyethyl methacrylate and 910 parts by
weight of glycidol. While air was supplied, the mixture was stirred
under reflux at 90.degree. C. for two hours to perform the
reaction.
[0289] After the reaction was complete, the reaction mixture was
purified through a column and was washed with ultrapure water, and
the solvent was removed. A hundred parts by weight of the resulting
resin was filtered through a column filled with 30 parts by weight
of a natural combination of quartz and kaolin (Sillitin V 85
available from Hoffmann Mineral GmbH) to allow it to adsorb ionic
impurities from the reaction product. The solvent was removed to
obtain Urethane-Modified Methacrylic Epoxy Resin (J).
[0290] Urethane-Modified Methacrylic Epoxy Resin (J) had a weight
average molecular weight Mw of 4,188 (as measured by GPC), a
hydrogen-bonding functional group value of 2.9.times.10.sup.-3
mol/g, and a carbon-carbon double bond content of
2.2.times.10.sup.-4 mol/g.
Preparation of Sealant
Sealant (1)
[0291] In 160 parts by weight of Modified Epoxy Resin (A), 100
parts by weight of an o-cresol novolac epoxy resin (EOCN-1020-20
available from Nippon Kayaku Co., Ltd.) was dissolved by heating to
obtain a homogeneous solution. After cooling, to the solution were
added 60 parts by weight of a hydrazide curing agent (Amicure VDH-J
available from Ajinomoto Fine-Techno Co., Inc.), serving as a
latent thermal curing agent, 4 parts by weight of an imidazole
curing agent (Curezol 2E4MZ-A available from Shikoku Chemicals
Corporation), serving as a latent thermal curing agent, 72 parts by
weight of spherical silica (Admafine AO-802 available from
Admatechs Co., Ltd.), serving as a filler, and 4 parts by weight of
a silane coupling agent (7-glycidoxypropyltrimethoxysilane, KBM-403
available from Shin-Etsu Chemical Co., Ltd.), serving as an
additive. The mixture was stirred in a planetary stirrer, was
milled on a ceramic three-roll mill, and was degassed and stirred
in a planetary stirrer to obtain Sealant (1). The properties of
Sealant (1) thus obtained are as follows:
[0292] Hydrogen-bonding functional group value (mol/g):
2.1.times.10.sup.-4
[0293] Resistivity of sealant before curing (.OMEGA.cm):
4.8.times.10.sup.6
[0294] Volume resistivity of sealant after curing (Qcm):
1.2.times.10.sup.13
Sealant (2)
[0295] A mixture was prepared from 100 parts by weight of a solid
o-cresol novolac epoxy resin (EOCN-1020-75 available from Nippon
Kayaku Co., Ltd., epoxy equivalent weight: 215 g/eq), 433 parts by
weight of PO-modified trisphenol triacrylate (molecular weight:
802, carbon-carbon double bond content: 0.0037 mol/g), and 217
parts by weight of Acrylic-Modified Epoxy Resin (B). The mixture
was dissolved by heating. To the solution were added 42 parts by
weight of a hydrazide curing agent (Amicure VDH available from
Ajinomoto Fine-Techno Co., Inc.), serving as a latent thermal
curing agent, 167 parts by weight of spherical silica (Seahostar
S-30 available from Nippon Shokubai Co., Ltd.), serving as a
filler, and 42 parts by weight of alkyl methacrylate copolymer
particles (F-325 available from Zeon Corporation). The mixture was
stirred in a planetary stirrer, was milled on a ceramic three-roll
mill, and was degassed and stirred in a planetary stirrer. To the
mixture was added 8.3 parts by weight of a thermal radical
polymerization initiator (Luperox 575 available from Arkema
Yoshitomi Ltd., 10-hour half-life temperature: 75.degree. C.). The
mixture was degassed and stirred in a planetary stirrer to obtain
Sealant (2). The properties of Sealant (2) thus obtained are as
follows:
[0296] Epoxy-to-(meth)acrylic equivalent ratio: 31:69
[0297] Hydrogen-bonding functional group value (mol/g):
7.4.times.10.sup.-4
[0298] Carbon-carbon double bond content (mol/g):
2.9.times.10.sup.-3
[0299] Resistivity of sealant before curing (Qcm):
7.7.times.10.sup.8
[0300] Volume resistivity of sealant after curing (Qcm):
1.5.times.10.sup.13
Sealant (3)
[0301] In 700 parts by weight of Monoacrylate-Modified Epoxy Resin
(C), 100 parts by weight of an o-cresol novolac epoxy resin
(EOCN-1020-55 available from Nippon Kayaku Co., Ltd.) was dissolved
by heating at 100.degree. C. for one hour to obtain a homogeneous
solution. After cooling, to the solution were added 800 parts by
weight of Diacrylate-Modified Epoxy Resin (D), 0.2 part of
p-benzoquinone (available from Seiko Chemical Co., Ltd.), 300 parts
by weight of spherical silica (Admafine A-802 available from
Admatechs Co., Ltd.), serving as an inorganic filler, 60 parts by
weight of a thermal latent epoxy curing agent (Amicure VDH-J
available from available from Ajinomoto Fine-Techno Co., Inc.), and
20 parts by weight of a silane coupling agent
(.gamma.-glycidoxypropyltrimethoxysilane, KBM-403 available from
Shin-Etsu Chemical Co., Ltd.), serving as an additive. The mixture
was stirred in a planetary stirrer, was milled on a ceramic
three-roll mill, and was degassed and stirred in a planetary
stirrer. To the mixture was added 20 parts by weight of a thermal
radical polymerization initiator (V-601 available from Wako Pure
Chemical Industries, Ltd., dimethyl 2,2'-azobis(isobutyrate),
10-hour half-life temperature: 66.degree. C.). The mixture was
degassed and stirred in a planetary stirrer to obtain 10 parts by
weight of Sealant (3). The properties of Sealant (3) thus obtained
are as follows:
[0302] Epoxy-to-(meth)acrylic equivalent ratio: 31:69
[0303] Hydrogen-bonding functional group value (mol/g):
3.2.times.10.sup.-3
[0304] Carbon-carbon double bond content (mol/g):
3.2.times.10.sup.-3
[0305] Resistivity of sealant before curing (.OMEGA.cm):
4.9.times.109
[0306] Volume resistivity of sealant after curing (.OMEGA.cm):
2.3.times.10.sup.13
Sealant (4)
[0307] A mixture was prepared from 70 parts by weight of a
bisphenol A epoxy resin (Epikote 828EL available from JER, epoxy
equivalent weight: 190 g/eq), 10 parts by weight of a thermal
latent epoxy curing agent (Amicure VDH available from Ajinomoto
Fine-Techno Co., Inc.), 3 parts by weight of an imidazole curing
agent (2-hydroxymethylimidazole), 30 parts by weight of
Acrylic-Modified Epoxy Resin (B), 15 parts by weight of silicon
dioxide (S-100 available from Nippon Shokubai Co., Ltd.), 20 parts
by weight of polymer particles (F.sub.325 available from Zeon Kasei
Co., Ltd., primary particle size: 0.5 .mu.m), and 0.5 part by
weight of a silane coupling agent
(.gamma.-glycidoxypropyltrimethoxysilane, KBM-403 available from
Shin-Etsu Chemical Co., Ltd.). The mixture was stirred in a
planetary stirrer, was milled on a ceramic three-roll mill, and was
degassed and stirred in a planetary stirrer to obtain Sealant (4).
The properties of Sealant (4) thus obtained are as follows:
[0308] Epoxy-to-(meth)acrylic equivalent ratio: 88:12
[0309] Hydrogen-bonding functional group value (mol/g):
7.7.times.10.sup.-4
[0310] Carbon-carbon double bond content (mol/g):
7.7.times.10.sup.-4
[0311] Resistivity of sealant before curing (.OMEGA.cm):
8.6.times.10.sup.7
[0312] Volume resistivity of sealant after curing (Qcm):
1.3.times.10.sup.13
Sealant (5)
[0313] A mixture was prepared from 25 parts by weight of a
diacrylate-modified bisphenol A epoxy resin (Epoxy Ester 3002A
available from Kyoeisha Chemical Co., Ltd., molecular weight: 600),
70 parts by weight of Acrylic-Modified Epoxy Resin (B), 5 parts by
weight of a solid o-cresol novolac epoxy resin (EOCN-1020-75
available from Nippon Kayaku Co., Ltd., epoxy equivalent weight:
215 g/eq), 5 parts by weight of a latent epoxy curing agent
(Amicure VDH available from Ajinomoto Fine-Techno Co., Inc.,
melting point: 120.degree. C.), and 20 parts by weight of spherical
silica (Seahostar S-30 available from Nippon Shokubai Co., Ltd.).
The mixture was stirred in a planetary stirrer, was milled on a
ceramic three-roll mill, and was degassed and stirred in a
planetary stirrer. To the mixture was added 1 part by weight of a
thermal radical polymerization initiator (Luperox 575 available
from Arkema Yoshitomi Ltd., 10-hour half-life temperature:
75.degree. C.). The mixture was degassed and stirred in a planetary
stirrer to obtain Sealant (5). The properties of Sealant (5) thus
obtained are as follows:
[0314] Epoxy-to-(meth)acrylic equivalent ratio: 43:57
[0315] Hydrogen-bonding functional group value (mol/g):
2.6.times.10.sup.-3
[0316] Carbon-carbon double bond content (mol/g):
2.6.times.10.sup.-3
[0317] Resistivity of sealant before curing (Qcm):
3.1.times.10.sup.9
[0318] Volume resistivity of sealant after curing (.OMEGA.cm):
2.1.times.10.sup.13
Sealant (6)
[0319] A mixture was prepared from 15 parts by weight of a solid
o-cresol novolac epoxy resin (EOCN-1020-75 available from Nippon
Kayaku Co., Ltd., epoxy equivalent weight: 215 g/eq) and 45 parts
by weight of a diacrylate-modified bisphenol A epoxy resin (Epoxy
Ester 3002A available from Kyoeisha Chemical Co., Ltd. molecular
weight: 600). The mixture was dissolved by heating at 100.degree.
C. for one hour to obtain a homogeneous solution. After cooling, to
the solution were added 20 parts by weight of Acrylic-Modified
Epoxy Resin (B), 0.5 part by weight of a radical chain transfer
agent (Karenz MT NR-1 available from Showa Denko K.K.,
1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)--
trione), 15 parts by weight of spherical silica (Seahostar S-30
available from Nippon Shokubai Co., Ltd.), 3 parts by weight of a
latent epoxy curing agent (Amicure VDH available from Ajinomoto
Fine-Techno Co., Inc., melting point: 120.degree. C.), and 1 part
by weight of a silane coupling agent
(.gamma.-glycidoxypropyltrimethoxysilane, KBM-403 available from
Shin-Etsu Chemical Co., Ltd.), serving as an additive. The mixture
was stirred in a planetary stirrer, was milled on a ceramic
three-roll mill, and was degassed and stirred in a planetary
stirrer. To the mixture was added 0.5 part by weight of a thermal
radical polymerization initiator (V-601 available from Wako Pure
Chemical Industries, Ltd., dimethyl 2,2'-azobis(isobutyrate),
10-hour half-life temperature: 66.degree. C.). The mixture was
vacuum-degassed and stirred in a planetary stirrer to obtain
Sealant (6). The properties of Sealant (6) thus obtained are as
follows:
[0320] Epoxy-to-(meth)acrylic equivalent ratio: 37:63
[0321] Hydrogen-bonding functional group value (mol/g):
2.51.times.10.sup.-3
[0322] Carbon-carbon double bond content (mol/g):
2.51.times.10.sup.-3
[0323] Resistivity of sealant before curing (.OMEGA.cm):
1.3.times.10.sup.9
[0324] Volume resistivity of sealant after curing (Qcm):
1.9.times.10.sup.13
Sealant (7)
[0325] A mixture was prepared from 20 parts by weight of
Diacrylate-Modified Epoxy Resin (E), 25 parts by weight of
Diacrylate-Modified Epoxy Resin (F), 25 parts by weight of
Diacrylate-Modified Epoxy Resin (G), 25 parts by weight of
Partially Acrylic-Modified Epoxy Resin (H), 5 parts by weight of a
solid o-cresol novolac epoxy resin (available from Nippon Kayaku
Co., Ltd., EOCN-1020-75, epoxy equivalent weight: 215 g/eq), 25
parts by weight of spherical silica (Seahostar S-30 available from
Nippon Shokubai Co., Ltd.), 8 parts by weight of a latent epoxy
curing agent (Amicure VDH available from Ajinomoto Fine-Techno Co.,
Inc.), and 2 parts by weight of alkyl methacrylate copolymer
particles (F-325 available from Zeon Corporation). The mixture was
stirred in a planetary stirrer, was milled on a ceramic three-roll
mill, and was degassed and stirred in a planetary stirrer. To the
mixture was added 1 part by weight of a thermal radical
polymerization initiator (V-65 available from Wako Pure Chemical
Industries, Ltd., 2,2'-azobis(2,4-dimethylvaleronitrile), 10-hour
half-life temperature: 51.degree. C.) The mixture was
vacuum-degassed and stirred in a planetary stirrer to obtain
Sealant (7). The properties of Sealant (7) thus obtained are as
follows:
[0326] Epoxy-to-(meth)acrylic equivalent ratio: 19:81
[0327] Carbon-carbon double bond content (mol/g):
3.01.times.10.sup.-3
[0328] Hydrogen-bonding functional group value (mol/g):
3.01.times.10.sup.-3
[0329] Resistivity of sealant before curing (.OMEGA.cm):
3.5.times.10.sup.9
[0330] Volume resistivity of sealant after curing (Qcm):
2.2.times.10.sup.13
Sealant (8)
[0331] A mixture was prepared from 50 parts by weight of
Methacrylic-Modified Bisphenol E Epoxy Resin (I), 50 parts by
weight of Urethane-Modified Methacrylic Epoxy Resin (J), 35 parts
by weight of spherical silica (SO--C1 available from Admatechs Co.,
Ltd.), 8 parts by weight of a latent epoxy curing agent (Amicure
VDH available from Ajinomoto Fine-Techno Co., Inc.), 1.5 parts by
weight of a silane coupling agent
(.gamma.-acryloxypropyltrimethoxysilane, KBM5103 available from
Shin-Etsu Chemical Co., Ltd.), and alkyl methacrylate copolymer
particles (F-325 available from Zeon Corporation). The mixture was
stirred in a planetary stirrer, was milled on a ceramic three-roll
mill, and was degassed and stirred in a planetary stirrer. To the
mixture was added 0.5 part by weight of a thermal radical
polymerization initiator (V-65 available from Wako Pure Chemical
Industries, Ltd., 10-hour half-life temperature: 51.degree. C.).
The mixture was vacuum-degassed and stirred in a planetary stirrer
to obtain Sealant (8). The properties of Sealant (8) thus obtained
are as follows:
[0332] Epoxy-to-(meth)acrylic equivalent ratio: 60:40
[0333] Carbon-carbon double bond content (mol/g):
1.26.times.10.sup.-3
[0334] Hydrogen-bonding functional group value (mol/g):
3.75.times.10.sup.-3
[0335] Resistivity of sealant before curing (.OMEGA.cm):
1.2.times.10.sup.9
[0336] Volume resistivity of sealant after curing (Qcm):
1.8.times.10.sup.-3
Comparative Sealant (C1)
[0337] A curable resin composition was prepared from 35 parts by
weight of urethane acrylate (AH-600 available from Kyoeisha
Chemical Co., Ltd.), 15 parts by weight of 2-hydroxybutyl acrylate,
50 parts by weight of isobornyl acrylate, and 0.5 part by weight of
a thermal radical polymerization initiator (V-65 available from
Wako Pure Chemical Industries, Ltd., 10-hour half-life temperature:
51.degree. C.). The curable resin composition was stirred in a
planetary stirrer and was uniformly milled on a ceramic three-roll
mill to obtain Comparative Sealant (C1), which was photocurable.
The properties of Comparative Sealant (C1) thus obtained are as
follows:
[0338] Hydrogen-bonding functional group value:
2.2.times.10.sup.-5
[0339] Resistivity of sealant before curing (Qcm):
5.0.times.10.sup.6
[0340] Volume resistivity of sealant after curing (.OMEGA.cm):
2.3.times.10.sup.13
Comparative Sealant (C2)
[0341] A curable resin composition was prepared from 50 parts by
weight of a bisphenol A epoxy resin (jER828US available from
Mitsubishi Chemical Corporation) and 25 parts by weight of a
hydrazide curing agent (NDH available from Japan Hydrazine Co.,
Ltd.). The curable resin composition was stirred in a planetary
stirrer and was uniformly milled on a ceramic three-roll mill to
obtain Comparative Sealant (C2). The properties of Comparative
Sealant (C2) thus obtained are as follows:
[0342] Hydrogen-bonding functional group value:
2.7.times.10.sup.-7
[0343] Resistivity of sealant before curing (.OMEGA.cm):
5.0.times.10.sup.10
[0344] Volume resistivity of sealant after curing (.OMEGA.cm):
3.0.times.10.sup.13
Examples 1 to 8
[0345] Transparent electrodes were formed on first and second
substrates. A black matrix (BM) was formed on the second substrate.
Vertical alignment layers (SE-5300) were formed on the opposing
surfaces of the two substrates and were subjected to an alignment
process. One of Sealants (1) to (8) was loaded into a syringe for
dispensing and was degassed. The sealant was applied to the
alignment layer on the first substrate using a dispenser to form a
rectangular frame pattern. Small droplets of Liquid Crystal
Composition 1 shown in the following table were dispensed over the
entire area within the frame pattern of the uncured sealant on the
first substrate, immediately followed by laminating the second
substrate in a vacuum of 5 Pa using a vacuum lamination system. The
drawing conditions and the gap between the substrates were
controlled so that, after the vacuum was released, the pressed
sealant had a line width of about 1.2 mm and overlapped the BM by
0.3 mm. The laminate was immediately heated in a
constant-temperature unit at 150.degree. C. for 90 minutes to cure
the sealant. In this way, VA liquid crystal display devices of
Examples 1 to 5 were fabricated (d.sub.gap=3.5 .mu.m). The
resulting liquid crystal display devices were tested for VHR and
were evaluated for alignment unevenness and image-sticking. The
results are shown in the following tables.
TABLE-US-00001 TABLE 1 Liquid Crystal Composition 1
T.sub.NI/.degree. C. 81.0 .DELTA.n 0.103 .DELTA..di-elect cons.
-2.9 .eta./mPa s 20.3 .gamma..sub.1/mPa s 112
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 105 3-Cy-Cy-2 24%
3-Cy-Cy-4 10% 3-Cy-Cy-5 5% 3-Cy-Ph--O1 2% 3-Cy-Ph5--O2 13%
2-Cy-Ph--Ph5--O2 9% 3-Cy-Ph--Ph5--O2 9% 3-Cy-Cy-Ph5--O3 5%
4-Cy-Cy-Ph5--O2 6% 5-Cy-Cy-Ph5--O2 5% 3-Ph--Ph5--Ph-2 6%
4-Ph--Ph5--Ph-2 6%
TABLE-US-00002 TABLE 2 Example 1 Example 2 Example 3 Example 4
Example 5 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition1 Composition1
Composition1 Composition1 Composition1 composition Sealant Sealant
(1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR 99.0 99.2
99.5 99.1 99.4 Alignment B A A B A unevenness Image- B B A A A
sticking
TABLE-US-00003 TABLE 3 Example 6 Example 7 Example 8 Liquid Liquid
Crystal Liquid Crystal Liquid Crystal crystal Composition1
Composition1 Composition1 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.3 99.5 99.3 Alignment A A A unevenness
Image- B A B sticking
[0346] Liquid Crystal Composition 1 was found to have a liquid
crystal layer temperature limit of 81.0.degree. C., which is
practical for television applications, a large absolute value of
dielectric anisotropy, a low viscosity, and a suitable
.DELTA.n.
[0347] The liquid crystal display devices of Examples 1 to 8 had
high VHRs and exhibited no or only slight and acceptable alignment
unevenness and image-sticking.
Examples 9 to 24
[0348] Liquid crystal display devices of Examples 9 to 24 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 2 and 3 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00004 TABLE 4 Liquid Crystal Composition 2
T.sub.NI/.degree. C. 76.0 .DELTA.n 0.103 .DELTA..di-elect cons.
-2.9 .eta./mPa s 19.8 .gamma..sub.1/mPa s 110
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 103 3-Cy-Cy-2 24%
3-Cy-Cy-4 10% 3-Cy-Ph--O1 7% 3-Cy-Ph5--O2 14% 2-Cy-Ph--Ph5--O2 7%
3-Cy-Ph--Ph5--O2 9% 3-Cy-Cy-Ph5--O3 5% 4-Cy-Cy-Ph5--O2 7%
5-Cy-Cy-Ph5--O2 5% 3-Ph--Ph5--Ph-2 6% 4-Ph--Ph5--Ph-2 6% Liquid
Crystal Composition 3 T.sub.NI/.degree. C. 84.8 .DELTA.n 0.103
.DELTA..di-elect cons. -2.9 .eta./mPa s 21.4 .gamma..sub.1/mPa s
119 .gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 112 3-Cy-Cy-2
24% 3-Cy-Cy-4 11% 3-Cy-Ph5--O2 12% 2-Cy-Ph--Ph5--O2 5%
3-Cy-Ph--Ph5--O2 6% 3-Cy-Cy-Ph5--O3 8% 4-Cy-Cy-Ph5--O2 8%
5-Cy-Cy-Ph5--O2 8% 3-Ph--Ph5--Ph-2 6% 4-Ph--Ph5--Ph-2 6% 5-Ph--Ph-1
3% 3-Cy-Cy-Ph-1 3%
TABLE-US-00005 TABLE 5 Example 9 Example 10 Example 11 Example 12
Example 13 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 2 Composition 2
Composition 2 Composition 2 Composition 2 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.3 99.6 99.2 99.5 Alignment B A A B A unevenness Image- B B
A B A sticking
TABLE-US-00006 TABLE 6 Example 14 Example 15 Example 16 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 2
Composition 2 Composition 2 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.5 99.6 99.4 Alignment B A B unevenness
Image- A A A sticking
TABLE-US-00007 TABLE 7 Example 17 Example 18 Example 19 Example 20
Example 21 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 3 Composition 3
Composition 3 Composition 3 Composition 3 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.0 99.2 99.6 99.1 99.4 Alignment B A A B A unevenness Image- B B
A B B sticking
TABLE-US-00008 TABLE 8 Example 22 Example 23 Example 24 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 3
Composition 3 Composition 3 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.4 99.5 99.3 Alignment A A B unevenness
Image- A A A sticking
[0349] Liquid Crystal Compositions 2 and 3 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0350] The liquid crystal display devices of Examples 9 to 24 had
high VHRs and exhibited no or only slight and acceptable alignment
unevenness and image-sticking.
Examples 25 to 48
[0351] Liquid crystal display devices of Examples 25 to 48 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 4 to 6 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00009 TABLE 9 Liquid Crystal Composition 4
T.sub.NI/.degree. C. 74.9 .DELTA.n 0.102 .DELTA..di-elect cons.
-2.9 .eta./mPa s 21.1 .gamma..sub.1/mPa s 118
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 111 3-Cy-Cy-2 22%
3-Cy-Cy-4 11% 3-Cy-Ph5--O2 7% 3-Cy-Ph5--O4 8% 2-Cy-Ph--Ph5--O2 6%
3-Cy-Ph--Ph5--O2 7% 3-Cy-Cy-Ph5--O3 7% 4-Cy-Cy-Ph5--O2 7%
5-Cy-Cy-Ph5--O2 7% 3-Ph--Ph5--Ph-2 4% 4-Ph--Ph5--Ph-2 4% 5-Ph--Ph-1
8% 3-Cy-Cy-Ph-1 2% Liquid Crystal Composition 5 T.sub.NI/.degree.
C. 80.2 .DELTA.n 0.105 .DELTA..di-elect cons. -2.9 .eta./mPa s 22.7
.gamma..sub.1/mPa s 124 .gamma..sub.1/.DELTA.n.sup.2 .times.
10.sup.-2 112 3-Cy-Cy-2 20% 3-Cy-Cy-4 10% 3-Cy-Ph5--O2 7%
3-Cy-Ph5--O4 7% 2-Cy-Ph--Ph5--O2 6% 3-Cy-Ph--Ph5--O2 7%
3-Cy-Cy-Ph5--O3 7% 4-Cy-Cy-Ph5--O2 8% 5-Cy-Cy-Ph5--O2 7%
3-Ph--Ph5--Ph-2 4% 4-Ph--Ph5--Ph-2 4% 5-Ph--Ph-1 8% 3-Cy-Cy-Ph-1 5%
Liquid Crystal Composition 6 T.sub.NI/.degree. C. 85.7 .DELTA.n
0.104 .DELTA..di-elect cons. -3.0 .eta./mPa s 22.9
.gamma..sub.1/mPa s 126 .gamma..sub.1/.DELTA.n.sup.2 .times.
10.sup.-2 116 3-Cy-Cy-2 20% 3-Cy-Cy-4 10% 3-Cy-Ph5--O2 7%
3-Cy-Ph5--O4 7% 2-Cy-Ph--Ph5--O2 6% 3-Cy-Ph--Ph5--O2 7%
3-Cy-Cy-Ph5--O3 7% 4-Cy-Cy-Ph5--O2 8% 5-Cy-Cy-Ph5--O2 7%
3-Ph--Ph5--Ph-2 4% 4-Ph--Ph5--Ph-2 4% 5-Ph--Ph-1 5% 3-Cy-Cy-Ph-1
8%
TABLE-US-00010 TABLE 10 Example 25 Example 26 Example 27 Example 28
Example 29 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 4 Composition 4
Composition 4 Composition 4 Composition 4 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.5 99.1 99.3 Alignment B B A B A unevenness Image- B A
A B A sticking
TABLE-US-00011 TABLE 11 Example 30 Example 31 Example 32 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 4
Composition 4 Composition 4 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.3 99.4 99.2 Alignment A A B unevenness
Image- B A A sticking
TABLE-US-00012 TABLE 12 Example 33 Example 34 Example 35 Example 36
Example 37 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 5 Composition 5
Composition 5 Composition 5 Composition 5 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
98.9 99.1 99.4 99.0 99.3 Alignment B B A B A unevenness Image- B A
A B A sticking
TABLE-US-00013 TABLE 13 Example 38 Example 39 Example 40 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 5
Composition 5 Composition 5 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.2 99.3 99.1 Alignment A A A unevenness
Image- B A B sticking
TABLE-US-00014 TABLE 14 Example 41 Example 42 Example 43 Example 44
Example 45 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 6 Composition 6
Composition 6 Composition 6 Composition 6 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.0 99.2 99.6 99.1 99.4 Alignment B B A A A unevenness Image- B A
A B A sticking
TABLE-US-00015 TABLE 15 Example 46 Example 47 Example 48 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 6
Composition 6 Composition 6 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.3 99.5 99.3 Alignment A A A unevenness
Image- A A B sticking
[0352] Liquid Crystal Compositions 4 to 6 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0353] The liquid crystal display devices of Examples 25 to 48 had
high VHRs and exhibited no or only slight and acceptable alignment
unevenness and image-sticking.
Examples 49 to 72
[0354] Liquid crystal display devices of Examples 49 to 72 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 7 to 9 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00016 TABLE 16 Liquid Crystal Composition 7
T.sub.NI/.degree. C. 75.1 .DELTA.n 0.103 .DELTA..di-elect cons.
-2.6 .eta./mPa s 20.5 .gamma..sub.1/mPa s 117
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 110 3-Cy-Cy-2 15%
3-Cy-Cy-4 12% 3-Cy-Cy-5 7% 3-Cy-Ph--O1 12% 3-Cy-Ph5--O2 6%
3-Cy-Ph5--O4 7% 2-Cy-Ph--Ph5--O2 11% 3-Cy-Ph--Ph5--O2 12%
3-Cy-Cy-Ph5--O3 3% 4-Cy-Cy-Ph5--O2 4% 5-Cy-Cy-Ph5--O2 3%
3-Ph--Ph5--Ph-2 4% 4-Ph--Ph5--Ph-2 4% Liquid Crystal Composition 8
T.sub.NI/.degree. C. 80.4 .DELTA.n 0.103 .DELTA..di-elect cons.
-2.6 .eta./mPa s 21.6 .gamma..sub.1/mPa s 125
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 117 3-Cy-Cy-2 15%
3-Cy-Cy-4 12% 3-Cy-Cy-5 7% 3-Cy-Ph--O1 12% 3-Cy-Ph5--O2 5%
3-Cy-Ph5--O4 5% 2-Cy-Ph--Ph5--O2 11% 3-Cy-Ph--Ph5--O2 11%
3-Cy-Cy-Ph5--O3 4% 4-Cy-Cy-Ph5--O2 6% 5-Cy-Cy-Ph5--O2 4%
3-Ph--Ph5--Ph-2 4% 4-Ph--Ph5--Ph-2 4% Liquid Crystal Composition 9
T.sub.NI/.degree. C. 85.1 .DELTA.n 0.103 .DELTA..di-elect cons.
-2.6 .eta./mPa s 22.7 .gamma..sub.1/mPa s 130
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 122 3-Cy-Cy-2 10%
3-Cy-Cy-4 15% 3-Cy-Cy-5 12% 3-Cy-Ph--O1 9% 3-Cy-Ph5--O2 5%
3-Cy-Ph5--O4 5% 2-Cy-Ph--Ph5--O2 11% 3-Cy-Ph--Ph5--O2 11%
3-Cy-Cy-Ph5--O3 4% 4-Cy-Cy-Ph5--O2 6% 5-Cy-Cy-Ph5--O2 4%
3-Ph--Ph5--Ph-2 4% 4-Ph--Ph5--Ph-2 4%
TABLE-US-00017 TABLE 17 Example 49 Example 50 Example 51 Example 52
Example 53 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 7 Composition 7
Composition 7 Composition 7 Composition 7 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.2 99.4 99.7 99.3 99.6 Alignment B B A B A unevenness Image- B A
A A A sticking
TABLE-US-00018 TABLE 18 Example 54 Example 55 Example 56 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 7
Composition 7 Composition 7 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.5 99.6 99.4 Alignment A A B unevenness
Image- A A A sticking
TABLE-US-00019 TABLE 19 Example 57 Example 58 Example 59 Example 60
Example 61 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 8 Composition 8
Composition 8 Composition 8 Composition 8 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.5 99.1 99.4 Alignment B A A B A unevenness Image- B B
A B A sticking
TABLE-US-00020 TABLE 20 Example 62 Example 63 Example 64 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 8
Composition 8 Composition 8 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.4 99.5 99.3 Alignment A A A unevenness
Image- A A B sticking
TABLE-US-00021 TABLE 21 Example 65 Example 66 Example 67 Example 68
Example 69 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 9 Composition 9
Composition 9 Composition 9 Composition 9 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.0 99.1 99.5 99.0 99.4 Alignment B B A B A unevenness Image- B B
A B B sticking
TABLE-US-00022 TABLE 22 Example 70 Example 71 Example 72 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 9
Composition 9 Composition 9 composition Sealant Sealant (6) Sealant
(7) Sealant (8) VHR 99.3 99.4 99.3 Alignment A A B unevenness
Image- B A A sticking
[0355] Liquid Crystal Compositions 7 to 9 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0356] The liquid crystal display devices of Examples 49 to 72 had
high VHRs and exhibited no or only slight and acceptable alignment
unevenness and image-sticking.
Examples 73 to 96
[0357] Liquid crystal display devices of Examples 73 to 96 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 10 to 12 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00023 TABLE 23 Liquid Crystal Composition 10
T.sub.NI/.degree. C. 76.7 .DELTA.n 0.109 .DELTA..di-elect cons.
-3.0 .eta./mPa s 22.4 .gamma..sub.1/mPa s 131
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 110 3-Cy-Cy-2 24%
3-Cy-Cy-4 6% 3-Cy-Ph--O1 5% 3-Cy-Ph5--O4 6% 3-Ph--Ph5--O2 6%
2-Cy-Ph--Ph5--O2 8% 3-Cy-Ph--Ph5--O2 8% 3-Cy-Cy-Ph5--O3 7%
4-Cy-Cy-Ph5--O2 9% 5-Cy-Cy-Ph5--O2 7% 3-Ph--Ph5--Ph-2 4%
4-Ph--Ph5--Ph-2 4% 5-Ph--Ph-1 6% Liquid Crystal Composition 11
T.sub.NI/.degree. C. 80.3 .DELTA.n 0.105 .DELTA..di-elect cons.
-3.1 .eta./mPa s 21.8 .gamma..sub.1/mPa s 126
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 114 3-Cy-Cy-2 24%
3-Cy-Cy-4 10% 3-Cy-Ph--O1 4% 3-Cy-Ph5--O4 6% 3-Ph--Ph5--O2 6%
2-Cy-Ph--Ph5--O2 8% 3-Cy-Ph--Ph5--O2 8% 3-Cy-Cy-Ph5--O3 7%
4-Cy-Cy-Ph5--O2 9% 5-Cy-Cy-Ph5--O2 7% 3-Ph--Ph5--Ph-2 4%
4-Ph--Ph5--Ph-2 4% 5-Ph--Ph-1 3% Liquid Crystal Composition 12
T.sub.NI/.degree. C. 85.8 .DELTA.n 0.104 .DELTA..di-elect cons.
-3.2 .eta./mPa s 22.0 .gamma..sub.1/mPa s 128
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 119 3-Cy-Cy-2 24%
3-Cy-Cy-4 10% 3-Cy-Ph--O1 4% 3-Cy-Ph5--O4 6% 3-Ph--Ph5--O2 6%
2-Cy-Ph--Ph5--O2 8% 3-Cy-Ph--Ph5--O2 8% 3-Cy-Cy-Ph5--O3 7%
4-Cy-Cy-Ph5--O2 9% 5-Cy-Cy-Ph5--O2 7% 3-Ph--Ph5--Ph-2 4%
4-Ph--Ph5--Ph-2 4% 3-Cy-Cy-Ph-1 3%
TABLE-US-00024 TABLE 24 Example 73 Example 74 Example 75 Example 76
Example 77 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 10 Composition 10
Composition 10 Composition 10 Composition 10 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.2 99.3 99.6 99.3 99.5 Alignment B B A A A unevenness Image- B A
A B A sticking
TABLE-US-00025 TABLE 25 Example 78 Example 79 Example 80 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 10
Composition 10 Composition 10 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.4 99.6 99.4 Alignment A A B
unevenness Image- A A A sticking
TABLE-US-00026 TABLE 26 Example 81 Example 82 Example 83 Example 84
Example 85 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 11 Composition 11
Composition 11 Composition 11 Composition 11 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.3 99.3 99.6 99.2 99.5 Alignment B A A B A unevenness Image- A B
A B A sticking
TABLE-US-00027 TABLE 27 Example 86 Example 87 Example 88 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 11
Composition 11 Composition 11 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.4 99.5 99.4 Alignment A A A
unevenness Image- B A B sticking
TABLE-US-00028 TABLE 28 Example 89 Example 90 Example 91 Example 92
Example 93 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 12 Composition 12
Composition 12 Composition 12 Composition 12 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.3 99.4 99.7 99.4 99.6 Alignment B A A A A unevenness Image- B B
A B A sticking
TABLE-US-00029 TABLE 29 Example 94 Example 95 Example 96 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 12
Composition 12 Composition 12 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.5 99.6 99.5 Alignment A A A
unevenness Image- A A B sticking
[0358] Liquid Crystal Compositions 10 to 12 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0359] The liquid crystal display devices of Examples 73 to 96 had
high VHRs and exhibited no or only slight and acceptable alignment
unevenness and image-sticking.
Examples 97 to 120
[0360] Liquid crystal display devices of Examples 97 to 120 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 13 to 15 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00030 TABLE 30 Liquid Crystal Composition 13
T.sub.NI/.degree. C. 71.9 .DELTA.n 0.116 .DELTA..di-elect cons.
-3.6 .eta./mPa s 21.2 .gamma..sub.1/mPa s 123
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 92 3-Cy-Cy-2 24%
3-Cy-Ph--O1 7% 2-Cy-Ph5--O2 6% 3-Cy-Ph5--O4 6% 3-Ph--Ph5--O2 5%
5-Ph--Ph5--O2 5% 2-Cy-Ph--Ph5--O2 7% 3-Cy-Ph--Ph5--O2 9%
3-Cy-Cy-Ph5--O3 5% 4-Cy-Cy-Ph5--O2 5% 5-Cy-Cy-Ph5--O2 4%
3-Ph--Ph5--Ph-2 5% 4-Ph--Ph5--Ph-2 6% 3-Cy-Cy-Ph-1 6% Liquid
Crystal Composition 14 T.sub.NI/.degree. C. 78.8 .DELTA.n 0.113
.DELTA..di-elect cons. -3.5 .eta./mPa s 21.1 .gamma..sub.1/mPa s
122 .gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 95 3-Cy-Cy-2 23%
3-Cy-Cy-4 5% 3-Cy-Ph--O1 3% 2-Cy-Ph5--O2 5% 3-Cy-Ph5--O4 5%
3-Ph--Ph5--O2 5% 5-Ph--Ph5--O2 5% 2-Cy-Ph--Ph5--O2 7%
3-Cy-Ph--Ph5--O2 7% 3-Cy-Cy-Ph5--O3 5% 4-Cy-Cy-Ph5--O2 6%
5-Cy-Cy-Ph5--O2 5% 3-Ph--Ph5--Ph-2 5% 4-Ph--Ph5--Ph-2 6%
3-Cy-Cy-Ph-1 8% Liquid Crystal Composition 15 T.sub.NI/.degree. C.
73.8 .DELTA.n 0.113 .DELTA..di-elect cons. -3.9 .eta./mPa s 21.8
.gamma..sub.1/mPa s 123 .gamma..sub.1/.DELTA.n.sup.2 .times.
10.sup.-2 97 3-Cy-Cy-2 16% 3-Cy-Cy-4 9% 3-Cy-Ph--O1 6% 2-Cy-Ph5--O2
6% 3-Cy-Ph5--O4 6% 3-Ph--Ph5--O2 6% 5-Ph--Ph5--O2 6%
2-Cy-Ph--Ph5--O2 5% 3-Cy-Ph--Ph5--O2 7% 3-Cy-Cy-Ph5--O3 5%
4-Cy-Cy-Ph5--O2 6% 5-Cy-Cy-Ph5--O2 6% 3-Ph--Ph5--Ph-2 5%
4-Ph--Ph5--Ph-2 5% 3-Cy-Cy-Ph-1 6%
TABLE-US-00031 TABLE 31 Example 97 Example 98 Example 99 Example
100 Example 101 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 13 Composition 13
Composition 13 Composition 13 Composition 13 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.6 99.1 99.4 Alignment B B A A B unevenness Image- B A
A B A sticking
TABLE-US-00032 TABLE 32 Example 102 Example 103 Example 104 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 13
Composition 13 Composition 13 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.4 99.6 99.3 Alignment B A A
unevenness Image- A A B sticking
TABLE-US-00033 TABLE 33 Example 105 Example 106 Example 107 Example
108 Example 109 Liquid Crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 14
Composition 14 Composition Composition Composition 14 14 14 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.2 99.3 99.5 99.2 99.4 Alignment B A A B A unevenness Image- B B
A B A sticking
TABLE-US-00034 TABLE 34 Example 110 Example 111 Example 112 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 14 Composition 14 Composition 14 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.4 99.5 99.3 Alignment A A A
unevenness Image-sticking A A B
TABLE-US-00035 TABLE 35 Example 113 Example 114 Example 115 Example
116 Example 117 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 15
Composition 15 Composition Composition Composition 15 15 15 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.0 99.1 99.5 99.0 99.4 Alignment B B A A A unevenness Image- B B
A B A sticking
TABLE-US-00036 TABLE 36 Example 118 Example 119 Example 120 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 15 Composition 15 Composition 15 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.5 99.3 Alignment A A A
unevenness Image-sticking A A B
[0361] Liquid Crystal Compositions 13 to 15 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0362] The liquid crystal display devices of Examples 97 to 120 had
high VHRs and exhibited no or only slight and acceptable alignment
unevenness and image-sticking.
Examples 121 to 144
[0363] Liquid crystal display devices of Examples 121 to 144 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 16 to 18 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00037 TABLE 37 Liquid Crystal Liquid Crystal Liquid
Crystal Composition 16 Composition 17 Composition 18
T.sub.NI/.degree. C. 75.9 T.sub.NI/.degree. C. 82.3
T.sub.NI/.degree. C. 85.7 .DELTA.n 0.112 .DELTA.n 0.111 .DELTA.n
0.112 .DELTA..epsilon. -2.8 .DELTA..epsilon. -2.7 .DELTA..epsilon.
-2.8 .eta./mPa s 19.8 .eta./mPa s 19.2 .eta./mPa s 20.1
.gamma..sub.1/mPa s 121 .gamma..sub.1/mPa s 114 .gamma..sub.1/mPa s
119 .gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 96
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 94
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 95 3-Cy-Cy-2 19%
3-Cy-Cy-2 21% 3-Cy-Cy-2 19% 3-Cy-Cy-4 12% 3-Cy-Cy-4 12% 3-Cy-Cy-4
12% 3-Cy-Cy-5 5% 3-Cy-Cy-5 5% 3-Cy-Cy-5 4% 3-Cy-Ph-O1 5%
2-Cy-Ph5-O2 4% 2-Cy-Ph5-O2 4% 2-Cy-Ph5-O2 4% 3-Cy-Ph5-O4 4%
3-Cy-Ph5-O4 4% 3-Cy-Ph5-O4 4% 3-Ph-Ph5-O2 3% 3-Ph-Ph5-O2 3%
3-Ph-Ph5-O2 3% 5-Ph-Ph5-O2 4% 5-Ph-Ph5-O2 4% 5-Ph-Ph5-O2 4%
2-Cy-Ph-Ph5-O2 6% 2-Cy-Ph-Ph5-O2 6% 2-Cy-Ph-Ph5-O2 6%
3-Cy-Ph-Ph5-O2 6% 3-Cy-Ph-Ph5-O2 6% 3-Cy-Ph-Ph5-O2 6%
3-Cy-Cy-Ph5-O3 5% 3-Cy-Cy-Ph5-O3 5% 3-Cy-Cy-Ph5-O3 5%
4-Cy-Cy-Ph5-O2 5% 4-Cy-Cy-Ph5-O2 5% 4-Cy-Cy-Ph5-O2 5%
5-Cy-Cy-Ph5-O2 4% 5-Cy-Cy-Ph5-O2 4% 5-Cy-Cy-Ph5-O2 5% 3-Ph-Ph5-Ph-2
7% 3-Ph-Ph5-Ph-2 7% 3-Ph-Ph5-Ph-2 8% 4-Ph-Ph5-Ph-2 8% 4-Ph-Ph5-Ph-2
8% 4-Ph-Ph5-Ph-2 9% 3-Cy-Cy-Ph-1 6% 3-Cy-Cy-Ph-1 9%
TABLE-US-00038 TABLE 38 Example 121 Example 122 Example 123 Example
124 Example 125 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 16
Composition 16 Composition Composition Composition 16 16 16 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.3 99.5 99.2 99.4 Alignment B A A B A unevenness Image- B B
A A A sticking
TABLE-US-00039 TABLE 39 Example 126 Example 127 Example 128 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 16 Composition 16 Composition 16 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.4 99.3 Alignment B A A
unevenness Image-sticking A A B
TABLE-US-00040 TABLE 40 Example 129 Example 130 Example 131 Example
132 Example 133 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 17
Composition 17 Composition Composition Composition 17 17 17 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.0 99.2 99.4 99.1 99.3 Alignment B A A A A unevenness Image- B B
A B B sticking
TABLE-US-00041 TABLE 41 Example 134 Example 135 Example 136 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 17 Composition 17 Composition 17 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.4 99.2 Alignment A A B
unevenness Image-sticking A A A
TABLE-US-00042 TABLE 42 Example 137 Example 138 Example 139 Example
140 Example 141 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 18
Composition 18 Composition Composition Composition 18 18 18 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.5 99.1 99.3 Alignment A B A A A unevenness Image- B A
A B B sticking
TABLE-US-00043 TABLE 43 Example 142 Example 143 Example 144 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 18 Composition 18 Composition 18 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.4 99.2 Alignment A A A
unevenness Image-sticking A A B
[0364] Liquid Crystal Compositions 16 to 18 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0365] The liquid crystal display devices of Examples 121 to 144
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Examples 145 to 168
[0366] Liquid crystal display devices of Examples 145 to 168 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 19 to 21 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00044 TABLE 44 Liquid Crystal Liquid Crystal Liquid
Crystal Composition 19 Composition 20 Composition 21
T.sub.NI/.degree. C. 77.1 T.sub.NI/.degree. C. 82.7
T.sub.NI/.degree. C. 86.4 .DELTA.n 0.104 .DELTA.n 0.107 .DELTA.n
0.106 .DELTA..epsilon. -3.5 .DELTA..epsilon. -3.0 .DELTA..epsilon.
-3.0 .eta./mPa s 25.1 .eta./mPa s 24.2 .eta./mPa s 24.4
.gamma..sub.1/mPa s 141 .gamma..sub.1/mPa s 141 .gamma..sub.1/mPa s
142 .gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 131
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 123
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 126 3-Cy-Cy-2 22%
3-Cy-Cy-2 24% 3-Cy-Cy-2 24% 3-Cy-Ph-O1 14% 3-Cy-Cy-4 5% 3-Cy-Cy-4
5% 2-Cy-Ph5-O2 7% 3-Cy-Ph-O1 6% 3-Cy-Ph-O1 6% 3-Cy-Ph5-O4 8%
2-Cy-Ph5-O2 5% 2-Cy-Ph5-O2 5% 2-Cy-Ph-Ph5-O2 7% 3-Cy-Ph5-O4 5%
3-Cy-Ph5-O4 5% 3-Cy-Ph-Ph5-O2 9% 2-Cy-Ph-Ph5-O2 7% 2-Cy-Ph-Ph5-O2
7% 3-Cy-Cy-Ph5-O3 8% 3-Cy-Ph-Ph5-O2 9% 3-Cy-Ph-Ph5-O2 9%
4-Cy-Cy-Ph5-O2 8% 3-Cy-Cy-Ph5-O3 8% 3-Cy-Cy-Ph5-O3 8%
5-Cy-Cy-Ph5-O2 8% 4-Cy-Cy-Ph5-O2 8% 4-Cy-Cy-Ph5-O2 8% 3-Ph-Ph5-Ph-2
5% 5-Cy-Cy-Ph5-O2 8% 5-Cy-Cy-Ph5-O2 8% 4-Ph-Ph5-Ph-2 4%
3-Ph-Ph5-Ph-2 5% 3-Ph-Ph5-Ph-2 5% 4-Ph-Ph5-Ph-2 5% 4-Ph-Ph5-Ph-2 5%
5-Ph-Ph-1 5% 5-Ph-Ph-1 3% 3-Cy-Cy-Ph-1 2%
TABLE-US-00045 TABLE 45 Example 145 Example 146 Example 147 Example
148 Example 149 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 19
Composition 19 Composition Composition Composition 19 19 19 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.2 99.3 99.6 99.3 99.5 Alignment B A A A A unevenness Image- B B
A B A sticking
TABLE-US-00046 TABLE 46 Example 150 Example 151 Example 152 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 19 Composition 19 Composition 19 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.4 99.5 99.4 Alignment A A A
unevenness Image-sticking B A B
TABLE-US-00047 TABLE 47 Example 153 Example 154 Example 155 Example
156 Example 157 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 20
Composition 20 Composition Composition Composition 20 20 20 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.3 99.4 99.7 99.4 99.6 Alignment B B A A A unevenness Image- B A
A B A sticking
TABLE-US-00048 TABLE 48 Example 158 Example 159 Example 160 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 20 Composition 20 Composition 20 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.5 99.6 99.5 Alignment A A B
unevenness Image-sticking A A A
TABLE-US-00049 TABLE 49 Example 161 Example 162 Example 163 Example
164 Example 165 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 21
Composition 21 Composition Composition Composition 21 21 21 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.0 99.1 99.4 99.1 99.3 Alignment A A A B A unevenness Image- B B
A B A sticking
TABLE-US-00050 TABLE 50 Example 166 Example 167 Example 168 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 21 Composition 21 Composition 21 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.4 99.2 Alignment B A B
unevenness Image-sticking A A A
[0367] Liquid Crystal Compositions 19 to 21 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0368] The liquid crystal display devices of Examples 145 to 168
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Examples 169 to 192
[0369] Liquid crystal display devices of Examples 169 to 192 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 22 to 24 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00051 TABLE 51 Liquid Crystal Liquid Crystal Liquid
Crystal Composition 22 Composition 23 Composition 24
T.sub.NI/.degree. C. 75.5 T.sub.NI/.degree. C. 80.3
T.sub.NI/.degree. C. 85.0 .DELTA.n 0.102 .DELTA.n 0.101 .DELTA.n
0.102 .DELTA..epsilon. -2.8 .DELTA..epsilon. -2.9 .DELTA..epsilon.
-3.0 .eta./mPa s 22.2 .eta./mPa s 22.0 .eta./mPa s 22.7
.gamma..sub.1/mPa s 121 .gamma..sub.1/mPa s 118 .gamma..sub.1/mPa s
122 .gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 117
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 117
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 118 3-Cy-Cy-2 14%
3-Cy-Cy-2 17% 3-Cy-Cy-2 16% 3-Cy-Cy-4 12% 3-Cy-Cy-4 12% 3-Cy-Cy-4
12% 3-Cy-Cy-5 5% 3-Cy-Cy-5 5% 3-Cy-Cy-5 5% 3-Cy-Ph-O1 7% 3-Cy-Ph-O1
6% 3-Cy-Ph-O1 5% 2-Cy-Ph5-O2 7% 2-Cy-Ph5-O2 12% 2-Cy-Ph5-O2 12%
3-Cy-Ph5-O4 7% 2-Cy-Ph-Ph5-O2 9% 2-Cy-Ph-Ph5-O2 9% 2-Cy-Ph-Ph5-O2
8% 3-Cy-Ph-Ph5-O2 9% 3-Cy-Ph-Ph5-O2 9% 3-Cy-Ph-Ph5-O2 8%
3-Cy-Cy-Ph5-O3 6% 3-Cy-Cy-Ph5-O3 6% 3-Cy-Cy-Ph5-O3 6%
4-Cy-Cy-Ph5-O2 8% 4-Cy-Cy-Ph5-O2 8% 4-Cy-Cy-Ph5-O2 7%
5-Cy-Cy-Ph5-O2 6% 5-Cy-Cy-Ph5-O2 6% 5-Cy-Cy-Ph5-O2 6% 3-Ph-Ph5-Ph-2
3% 3-Ph-Ph5-Ph-2 3% 3-Ph-Ph5-Ph-2 3% 4-Ph-Ph5-Ph-2 3% 4-Ph-Ph5-Ph-2
3% 4-Ph-Ph5-Ph-2 3% 5-Ph-Ph-1 4% 5-Ph-Ph-1 3% 5-Ph-Ph-1 6%
3-Cy-Cy-Ph-1 3% 3-Cy-Cy-Ph-1 1%
TABLE-US-00052 TABLE 52 Example 169 Example 170 Example 171 Example
172 Example 173 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 22
Composition 22 Composition Composition Composition 22 22 22 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant 5) VHR 99.0
99.2 99.5 99.2 99.4 Alignment B A A A A unevenness Image- B B A B B
sticking
TABLE-US-00053 TABLE 53 Example 174 Example 175 Example 176 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 22 Composition 22 Composition 22 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.5 99.3 Alignment A A A
unevenness Image-sticking B A A
TABLE-US-00054 TABLE 54 Example 177 Example 178 Example 179 Example
180 Example 181 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 23
Composition 23 Composition Composition Composition 23 23 23 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.5 99.1 99.4 Alignment A B A B A unevenness Image- B A
A B A sticking
TABLE-US-00055 TABLE 55 Example 182 Example 183 Example 184 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 23 Composition 23 Composition 23 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.5 99.3 Alignment A A A
unevenness Image-sticking B A B
TABLE-US-00056 TABLE 56 Example 185 Example 186 Example 187 Example
188 Example 189 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 24
Composition 24 Composition Composition Composition 24 24 24 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.3 99.4 99.7 99.3 99.6 Alignment B B A B A unevenness Image- B A
A A A sticking
TABLE-US-00057 TABLE 57 Example 190 Example 191 Example 192 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 24 Composition 24 Composition 24 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.5 99.7 99.5 Alignment A A B
unevenness Image-sticking A A A
[0370] Liquid Crystal Compositions 22 to 24 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0371] The liquid crystal display devices of Examples 169 to 192
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Examples 193 to 216
[0372] Liquid crystal display devices of Examples 193 to 216 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 25 to 27 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00058 TABLE 58 Liquid Crystal Liquid Crystal Liquid
Crystal Composition 25 Composition 26 Composition 27
T.sub.NI/.degree.C. 75.6 T.sub.NI/.degree.C. 81.1
T.sub.NI/.degree.C. 85.7 .DELTA.n 0.104 .DELTA.n 0.105 .DELTA.n
0.105 .DELTA..epsilon. -2.8 .DELTA..epsilon. -2.8 .DELTA..epsilon.
-2.9 .eta./mPa s 20.2 .eta./mPa s 20.8 .eta./mPa s 21.0
.gamma..sub.1/mPa s 117 .gamma..sub.1/mPa s 119 .gamma..sub.1/mPa s
92 .gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 107
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 107
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 82 3-Cy-Cy-2 25%
3-Cy-Cy-2 25% 3-Cy-Cy-2 25% 3-Cy-Cy-4 10% 3-Cy-Cy-4 10% 3-Cy-Cy-4
12% 3-Cy-Ph-O1 4% 3-Cy-Ph-O1 4% 2-Cy-Ph5-O2 12% 2-Cy-Ph5-O2 7%
2-Cy-Ph5-O2 12% 2-Cy-Ph-Ph5-O2 5% 3-Cy-Ph5-O4 8% 2-Cy-Ph-P5-O2 5%
3-Cy-Ph-Ph5-O2 6% 2-Cy-Ph-Ph5-O2 5% 3-Cy-Ph-Ph5-O2 6%
3-Cy-Cy-Ph5-O3 7% 3-Cy-Ph-Ph5-O2 6% 3-Cy-Cy-Ph5-O3 7%
4-Cy-Cy-Ph5-O2 8% 3-Cy-Cy-Ph5-O3 6% 4-Cy-Cy-Ph5-O2 8%
5-Cy-Cy-Ph5-O2 7% 4-Cy-Cy-Ph5-O2 7% 5-Cy-Cy-Ph5-O2 7% 3-Ph-Ph5-Ph-2
8% 5-Cy-Cy-Ph5-O2 6% 3-Ph-Ph5-Ph-2 8% 4-Ph-Ph5-Ph-2 8%
3-Ph-Ph5-Ph-2 8% 4-Ph-Ph5-Ph-2 8% 3-Cy-Cy-Ph-1 2% 4-Ph-Ph5-Ph-2
8%
TABLE-US-00059 TABLE 59 Example 193 Example 194 Example 195 Example
196 Example 197 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 25
Composition 25 Composition Composition Composition 25 25 25 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.4 99.5 99.8 99.5 99.6 Alignment A A A B A unevenness Image- B B
A B B sticking
TABLE-US-00060 TABLE 60 Example 198 Example 199 Example 200 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 25 Composition 25 Composition 25 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.6 99.7 99.5 Alignment A A B
unevenness Image-sticking B A A
TABLE-US-00061 TABLE 61 Example 201 Example 202 Example 203 Example
204 Example 205 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 26
Composition 26 Composition Composition Composition 26 26 26 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.2 99.4 99.6 99.3 99.5 Alignment B B A A A unevenness Image- B A
A B A sticking
TABLE-US-00062 TABLE 62 Example 206 Example 207 Example 208 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 26 Composition 26 Composition 26 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.5 99.6 99.4 Alignment A A B
unevenness Image-sticking A A A
TABLE-US-00063 TABLE 63 Example 209 Example 210 Example 211 Example
212 Example 213 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 27 Composition 27
Composition 27 Composition 27 Composition 27 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.5 99.1 99.4 Alignment A A A B A unevenness Image- B B
A B A sticking
TABLE-US-00064 TABLE 64 Example 214 Example 215 Example 216 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 27
Composition 27 Composition 27 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.4 99.3 Alignment B A A
unevenness Image- A A A sticking
[0373] Liquid Crystal Compositions 25 to 27 were found to have
practical liquid crystal layer temperature limits for television
applications, large absolute values of dielectric anisotropy, low
viscosities, and suitable .DELTA.n.
[0374] The liquid crystal display devices of Examples 193 to 216
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Examples 217 to 224
[0375] Liquid Crystal Composition 1 was mixed with 0.3% by mass of
4-{2-[4-(2-acryloyloxyethyl)phenoxycarbonyl]ethyl}biphenyl-4'-yl
2-methylacrylate to obtain Liquid Crystal Composition 28. Liquid
Crystal Composition 28 was sandwiched and sealed using one of
Sealants (1) to (8) as in Example 1. The liquid crystal composition
was polymerized by exposure to UV radiation for 600 seconds (3.0
J/cm.sup.2) with a drive voltage being applied across the
electrodes. In this way, PSVA liquid crystal display devices of
Examples 217 to 224 were fabricated. The resulting liquid crystal
display devices were tested for VHR and were evaluated for
alignment unevenness and image-sticking. The results are shown in
the following tables.
TABLE-US-00065 TABLE 65 Example 217 Example 218 Example 219 Example
220 Example 221 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 28 Composition 28
Composition 28 Composition 28 Composition 28 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.0 99.2 99.4 99.1 99.4 Alignment B A A A B unevenness Image- B B
A B A sticking
TABLE-US-00066 TABLE 66 Example 222 Example 223 Example 224 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 28
Composition 28 Composition 28 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.4 99.2 Alignment A A B
unevenness Image- A A B sticking
[0376] The liquid crystal display devices of Examples 217 to 224
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Examples 225 to 232
[0377] Liquid Crystal Composition 13 was mixed with 0.3% by mass of
biphenyl-4,4'-diyl bismethacrylate to obtain Liquid Crystal
Composition 29. Liquid Crystal Composition 29 was sandwiched and
sealed using one of Sealants (1) to (8) as in Example 1. The liquid
crystal composition was polymerized by exposure to UV radiation for
600 seconds (3.0 J/cm.sup.2) with a drive voltage being applied
across the electrodes. In this way, PSVA liquid crystal display
devices of Examples 225 to 232 were fabricated. The resulting
liquid crystal display devices were tested for VHR and were
evaluated for alignment unevenness and image-sticking. The results
are shown in the following tables.
TABLE-US-00067 TABLE 67 Example 225 Example 226 Example 227 Example
228 Example 229 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 29 Composition 29
Composition 29 Composition 29 Composition 29 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.5 99.2 99.5 Alignment A A A A A unevenness Image- B B
A B A sticking
TABLE-US-00068 TABLE 68 Example 230 Example 231 Example 232 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 29
Composition 29 Composition 29 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.4 99.5 99.3 Alignment B A B
unevenness Image- A A A sticking
[0378] The liquid crystal display devices of Examples 225 to 232
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Examples 233 to 240
[0379] Liquid Crystal Composition 19 was mixed with 0.3% by mass of
3-fluorobiphenyl-4,4'-diyl bismethacrylate to obtain Liquid Crystal
Composition 30. Liquid Crystal Composition 30 was sandwiched and
sealed using one of Sealants (1) to (8) as in Example 1. The liquid
crystal composition was polymerized by exposure to UV radiation for
600 seconds (3.0 J/cm.sup.2) with a drive voltage being applied
across the electrodes. In this way, PSVA liquid crystal display
devices of Examples 233 to 240 were fabricated. The resulting
liquid crystal display devices were tested for VHR and were
evaluated for alignment unevenness and image-sticking. The results
are shown in the following tables.
TABLE-US-00069 TABLE 69 Example 233 Example 234 Example 235 Example
236 Example 237 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 30 Composition 30
Composition 30 Composition 30 Composition 30 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.2 99.3 99.6 99.3 99.5 Alignment B A A A A unevenness Image- B B
A B A sticking
TABLE-US-00070 TABLE 70 Example 238 Example 239 Example 240 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 30
Composition 30 Composition 30 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.4 99.6 99.4 Alignment A A A
unevenness Image- A A B sticking
[0380] The liquid crystal display devices of Examples 233 to 240
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Examples 241 to 264
[0381] Liquid crystal display devices of Examples 241 to 264 were
fabricated using Sealants (1) to (8) as in Example 1 except that
Liquid Crystal Compositions 31 to 33 shown in the following tables
were sandwiched therein. The resulting liquid crystal display
devices were tested for VHR and were evaluated for alignment
unevenness and image-sticking. The results are shown in the
following tables.
TABLE-US-00071 TABLE 71 Liquid Crystal Composition 31 TNI/.degree.
C. 75.5 .DELTA.n 0.103 .DELTA..di-elect cons. -3.1 .eta./mPa s 15.8
.gamma.1/mPa s 113 .gamma.1/.DELTA.n2 .times. 10-2 113 3-Cy-Cy-2
13% 3-Cy-Cy-V1 12% 3-Cy-Cy-4 5% 3-Ph--Ph-1 3% 5-Ph--Ph-1 12%
3-Cy-Cy-Ph-1 3% V-Cy-Ph--Ph-3 6% 3-Cy-1O--Ph5--O2 11%
2-Cy-Cy-1O--Ph5--O2 12% 3-Cy-Cy-1O--Ph5--O2 12% 4-Cy-Cy-1O--Ph5--O2
2% V-Cy-Cy-1O--Ph5--O2 3% 1V-Cy-Cy-1O--Ph5--O2 6% Liquid Crystal
Composition 32 TNI/.degree. C. 75.4 .DELTA.n 0.109 .DELTA..di-elect
cons. -3.1 .eta./mPa s 14.9 .gamma.1/mPa s 110 .gamma.1/.DELTA.n2
.times. 10-2 92 2-Cy-Cy-V1 20% 3-Cy-Cy-V1 13% 3-Ph--Ph-1 10%
5-Ph--Ph-1 5% 3-Cy-Ph--Ph-2 6% 1V-Cy-1O--Ph5--O2 8%
2-Cy-Cy-1O--Ph5--O2 10% 3-Cy-Cy-1O--Ph5--O2 10% V-Cy-Cy-1O--Ph5--O2
10% 1V-Cy-Cy-1O--Ph5--O2 4% 3-Ph--Ph5--Ph-2 4% Liquid Crystal
Composition 33 TNI/.degree. C. 83.1 .DELTA.n 0.114 .DELTA..di-elect
cons. -2.9 .eta./mPa s 14.8 .gamma.1/mPa s 92 .gamma.1/.DELTA.n2
.times. 10-2 71 V2--Ph--Ph-1 5% 3-Cy-Cy-V 39% 3-Cy-1O--Ph5--O2 5%
2-Cy-Cy-1O--Ph5--O2 11% 3-Cy-Cy-1O--Ph5--O1 11% 3-Cy-Cy-1O--Ph5--O2
6% 2-Cy-Ph--Ph5--O2 6% 3-Ph--Ph5--Ph-1 8% 3-Ph--Ph5--Ph-2 9%
TABLE-US-00072 TABLE 72 Example 241 Example 242 Example 243 Example
244 Example 245 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 31 Composition 31
Composition 31 Composition 31 Composition 31 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.6 99.1 99.5 Alignment A A A B A unevenness Image- B B
A B A sticking
TABLE-US-00073 TABLE 73 Example 246 Example 247 Example 248 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 31
Composition 31 Composition 31 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.4 99.6 99.3 Alignment A A A
unevenness Image- A A B sticking
TABLE-US-00074 TABLE 74 Example 249 Example 250 Example 251 Example
252 Example 253 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 32 Composition 32
Composition 32 Composition 32 Composition 32 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.2 99.2 99.5 99.2 99.4 Alignment A B A A A unevenness Image- B B
A B B sticking
TABLE-US-00075 TABLE 75 Example 254 Example 255 Example 256 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 32
Composition 32 Composition 32 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.5 99.3 Alignment A A B
unevenness Image- B A A sticking
TABLE-US-00076 TABLE 76 Example 257 Example 258 Example 259 Example
260 Example 261 Liquid Liquid Crystal Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal crystal Composition 33 Composition 33
Composition 33 Composition 33 Composition 33 composition Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
98.9 99.1 99.4 99.0 99.3 Alignment B B A B A unevenness Image- B B
A A B sticking
TABLE-US-00077 TABLE 77 Example 262 Example 263 Example 264 Liquid
Liquid Crystal Liquid Crystal Liquid Crystal crystal Composition 33
Composition 33 Composition 33 composition Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.2 99.3 99.2 Alignment A A A
unevenness Image- B B B sticking
[0382] The liquid crystal display devices of Examples 241 to 264
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Examples 265 to 280
[0383] Liquid crystal display devices of Examples 265 to 280 were
fabricated as in Example 1 except that the liquid crystal
composition and polymerizable liquid crystal composition shown in
the following tables were used. The resulting liquid crystal
display devices were tested for VHR and ID and were evaluated for
image-sticking. The results are shown in the following tables.
TABLE-US-00078 TABLE 78 Liquid Crystal Composition 34 Liquid
Crystal Composition 35 TNI/.degree. C. 76.3 TNI/.degree. C. 76.6
.DELTA.n 0.106 .DELTA.n 0.109 .DELTA..epsilon. -3.0
.DELTA..epsilon. -3.2 .eta./mPa s 16.6 .eta./mPa s 13.9
.gamma.1/mPa s 106 .gamma.1/mPa s 95 .gamma.1/.DELTA.n2 .times.
10-2 95 .gamma.1/.DELTA.n2 .times. 10-2 80 3-Cy-Cy-2 17%
1V-Cy-1O-Ph5-O2 12% 3-Cy-Ph-Ph-2 12% 1V-Cy-Cy-1O-Ph5-O2 12%
3-Cy-1O-Ph5-O1 11% 3-Cy-1O-Ph5-O2 2% 3-Cy-1O-Ph5-O2 17%
2-Cy-Cy-1O-Ph5-O2 5% 3-Nd-Ph5-Ph-2 4% 3-Cy-Cy-1O-Ph5-O2 4%
3-Cy-Cy-V 5% 3-Cy-Ph-Ph5-O2 4% 3-Cy-Cy-V1 10% 3-Cy-Cy-V 38%
V-Cy-Ph-Ph-3 12% 3-Cy-Cy-V1 3% V-Cy-Cy-1O-Ph5-O3 12% 3-Ph-Ph-1 3%
V2-Ph-Ph5-Ph-2V 12% 1V2-Ph-Ph5-Ph2-V1 5%
TABLE-US-00079 TABLE 79 Example 265 Example 266 Example 267 Example
268 Example 269 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 34
Composition 34 Composition Composition Composition 34 34 34 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.1 99.2 99.5 99.2 99.4 Alignment B A A B A unevenness Image- B B
A B A sticking
TABLE-US-00080 TABLE 80 Example 270 Example 271 Example 272 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 34 Composition 34 Composition 34 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.5 99.3 Alignment B A B
unevenness Image-sticking A A A
TABLE-US-00081 TABLE 81 Example 273 Example 274 Example 275 Example
276 Example 277 Liquid crystal Liquid Crystal Liquid Crystal Liquid
Crystal Liquid Crystal Liquid Crystal composition Composition 35
Composition 35 Composition Composition Composition 35 35 35 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
99.0 99.1 99.4 99.1 99.4 Alignment B A A B A unevenness Image- B B
A B A sticking
TABLE-US-00082 TABLE 82 Example 278 Example 279 Example 280 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal composition
Composition 35 Composition 35 Composition 35 Sealant Sealant (6)
Sealant (7) Sealant (8) VHR 99.3 99.4 99.2 Alignment A A A
unevenness Image-sticking B A B
[0384] The liquid crystal display devices of Examples 265 to 280
had high VHRs and exhibited no or only slight and acceptable
alignment unevenness and image-sticking.
Comparative Examples 1 to 15
[0385] VA liquid crystal display devices of Comparative Examples 1
to 15 were fabricated as in Example 1 except that Liquid Crystal
Composition 1 was replaced with Comparative Liquid Crystal
Compositions 1 to 3 shown in the following tables. The resulting
liquid crystal display devices were tested for VHR and were
evaluated for alignment unevenness and image-sticking. The results
are shown in the following tables.
TABLE-US-00083 TABLE 83 Comparative Comparative Comparative Liquid
Crystal Liquid Crystal Liquid Crystal Composition 1 Composition 2
Composition 3 3-Cy-Cy-2 4% 3-Cy-Cy-2 4% 3-Cy-Cy-2 4% 3-Cy-Cy-4 4%
3-Cy-Cy-4 4% 3-Cy-Cy-4 4% 3-Cy-Ph5-O2 7% 3-Cy-Ph5-O2 7% 3-Cy-Ph5-
7% O2 3-Cy-Ph5-O4 8% 3-Cy-Ph5-O4 8% 3-Cy-Ph5- 8% O4 2-Cy-Ph-Ph5-O2
4% 2-Cy-Ph-Ph5-O2 5% 2-Cy-Ph- 6% Ph5-O2 3-Cy-Ph-Ph5-O2 5%
3-Cy-Ph-Ph5-O2 6% 3-Cy-Ph- 7% Ph5-O2 3-Cy-Cy-Ph5-O3 8%
3-Cy-Cy-Ph5-O3 7% 3-Cy-Cy- 7% Ph5-O3 4-Cy-Cy-Ph5-O2 10%
4-Cy-Cy-Ph5-O2 9% 4-Cy-Cy- 7% Ph5-O2 5-Cy-Cy-Ph5-O2 8%
5-Cy-Cy-Ph5-O2 7% 5-Cy-Cy- 7% Ph5-O2 3-Ph-Ph5-Ph-2 4% 3-Ph-Ph5-Ph-2
4% 3-Ph-Ph5- 4% Ph-2 4-Ph-Ph5-Ph-2 4% 4-Ph-Ph5-Ph-2 4% 4-Ph-Ph5- 4%
Ph-2 5-Ph-Ph-1 25% 5-Ph-Ph-1 22% 5-Ph-Ph-1 19% 3-Cy-Cy-Ph-1 9%
3-Cy-Cy-Ph-1 13% 3-Cy-Cy- 16% Ph-1
TABLE-US-00084 TABLE 84 Comparative Comparative Comparative
Comparative Comparative Example 1 Example 2 Example 3 Example 4
Example 5 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 1
Composition 1 Composition 1 Composition 1 Composition 1 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.3 97.5 98.0 97.4 97.8 Alignment D D C D C unevenness Image- D D
C D D sticking
TABLE-US-00085 TABLE 85 Comparative Comparative Comparative Example
6 Example 7 Example 8 Liquid crystal Comparative Comparative
Comparative composition Liquid Crystal Liquid Crystal Liquid
Crystal Composition 1 Composition 1 Composition 1 Sealant Sealant
(6) Sealant (7) Sealant (8) VHR 97.7 97.8 97.5 Alignment C C C
unevenness Image-sticking D C D
TABLE-US-00086 TABLE 86 Comparative Comparative Comparative
Comparative Comparative Example 9 Example 10 Example 11 Example 12
Example 13 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 2
Composition 2 Composition 2 Composition 2 Composition 2 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.4 97.5 98.1 97.5 97.9 Alignment D D C D D unevenness Image- D D
C D C sticking
TABLE-US-00087 TABLE 87 Comparative Comparative Comparative Example
14 Example 15 Example 16 Liquid crystal Comparative Comparative
Comparative composition Liquid Crystal Liquid Crystal Liquid
Crystal Composition 2 Composition 2 Composition 2 Sealant Sealant
(6) Sealant (7) Sealant (8) VHR 97.7 98.0 97.6 Alignment D C D
unevenness Image-sticking D D D
TABLE-US-00088 TABLE 88 Comparative Comparative Comparative
Comparative Comparative Example 17 Example 18 Example 19 Example 20
Example 21 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 3
Composition 3 Composition 3 Composition 3 Composition 3 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.2 97.5 98.1 97.3 97.9 Alignment D C C D C unevenness Image- D D
C D D sticking
TABLE-US-00089 TABLE 89 Comparative Comparative Comparative Example
22 Example 23 Example 24 Liquid crystal Comparative Comparative
Comparative composition Liquid Crystal Liquid Crystal Liquid
Crystal Composition 3 Composition 3 Composition 3 Sealant Sealant
(6) Sealant (7) Sealant (8) VHR 97.8 98.0 97.6 Alignment C C D
unevenness Image-sticking D C D
[0386] The liquid crystal display devices of Comparative Examples 1
to 24 had lower VHRs than those according to the present invention
and exhibited unacceptable alignment unevenness and
image-sticking.
Comparative Examples 25 to 48
[0387] VA liquid crystal display devices of Comparative Examples 25
to 48 were fabricated as in Comparative Example 1 except that
Comparative Liquid Crystal Composition 1 was replaced with
Comparative Liquid Crystal Compositions 4 to 6 shown in the
following tables. The resulting liquid crystal display devices were
tested for VHR and were evaluated for alignment unevenness and
image-sticking. The results are shown in the following tables.
TABLE-US-00090 TABLE 90 Comparative Liquid Crystal Comparative
Liquid Crystal Comparative Liquid Crystal Composition 4 Composition
5 Composition 6 T.sub.NI/.degree. C. 73.6 T.sub.NI/.degree. C. 80.9
T.sub.NI/.degree. C. 84.7 .DELTA.n 0.099 .DELTA.n 0.094 .DELTA.n
0.085 .DELTA..epsilon. -2.15 .DELTA..epsilon. -2.16
.DELTA..epsilon. -2.13 .eta./mPa s 17.7 .eta./mPa s 17.0 .eta./mPa
s 17.5 .gamma..sub.1/mPa s 104 .gamma..sub.1/mPa s 97
.gamma..sub.1/mPa s 98 .gamma..sub.1/.DELTA.n.sup.2 .times.
10.sup.-2 106 .gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 109
.gamma..sub.1/.DELTA.n.sup.2 .times. 10.sup.-2 136 3-Cy-Cy-2 20%
3-Cy-Cy-2 24% 3-Cy-Cy-2 21% 3-Cy-Cy-4 12% 3-Cy-Cy-4 12% 3-Cy-Cy-4
15% 3-Cy-Cy-5 7% 3-Cy-Cy-5 15% 3-Cy-Cy-5 15% 3-Cy-Ph-O1 12%
3-Cy-Ph5-O2 5% 3-Cy-Ph5-O2 5% 3-Cy-Ph5-O2 5% 3-Cy-Ph5-O4 5%
3-Cy-Ph5-O4 5% 3-Cy-Ph5-O4 5% 2-Cy-Ph-Ph5-O2 11% 2-Cy-Ph-Ph5-O2 4%
2-Cy-Ph-Ph5-O2 11% 3-Cy-Ph-Ph5-O2 11% 3-Cy-Ph-Ph5-O2 5%
3-Cy-Ph-Ph5-O2 11% 3-Cy-Cy-Ph5-O3 3% 3-Cy-Cy-Ph5-O3 7%
3-Cy-Cy-Ph5-O3 3% 4-Cy-Cy-Ph5-O2 3% 4-Cy-Cy-Ph5-O2 8%
4-Cy-Cy-Ph5-O2 3% 5-Cy-Cy-Ph5-O2 3% 5-Cy-Cy-Ph5-O2 7%
5-Cy-Cy-Ph5-O2 3% 3-Ph-Ph5-Ph-2 4% 3-Ph-Ph5-Ph-2 4% 3-Ph-Ph5-Ph-2
4% 4-Ph-Ph5-Ph-2 4% 4-Ph-Ph5-Ph-2 4% 4-Ph-Ph5-Ph-2 4%
TABLE-US-00091 TABLE 91 Comparative Comparative Comparative
Comparative Comparative Example 25 Example 26 Example 27 Example 28
Example 29 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 4
Composition 4 Composition 4 Composition 4 Composition 4 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.1 97.2 98.0 97.1 97.7 Alignment D D C D C unevenness Image- D D
C C D sticking
TABLE-US-00092 TABLE 92 Comparative Comparative Comparative Example
30 Example 31 Example 32 Liquid crystal Comparative Comparative
Comparative composition Liquid Crystal Liquid Crystal Liquid
Crystal Composition 4 Composition 4 Composition 4 Sealant Sealant
(6) Sealant (7) Sealant (8) VHR 97.6 97.8 97.4 Alignment C C D
unevenness Image-sticking D D C
TABLE-US-00093 TABLE 93 Comparative Comparative Comparative
Comparative Comparative Example 33 Example 34 Example 35 Example 36
Example 37 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 5
Composition 5 Composition 5 Composition 5 Composition 5 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.2 97.3 98.1 97.3 97.8 Alignment D C C D C unevenness Image- D D
C D D sticking
TABLE-US-00094 TABLE 94 Comparative Comparative Comparative Example
38 Example 30 Example 40 Liquid crystal Comparative Comparative
Comparative composition Liquid Crystal Liquid Crystal Liquid
Crystal Composition 5 Composition 5 Composition 5 Sealant Sealant
(6) Sealant (7) Sealant (8) VHR 97.7 98.0 97.5 Alignment C C C
unevenness Image-sticking D C D
TABLE-US-00095 TABLE 95 Comparative Comparative Comparative
Comparative Comparative Example 41 Example 42 Example 43 Example 44
Example 45 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 6
Composition 6 Composition 6 Composition 6 Composition 6 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.1 97.2 97.9 97.1 97.6 Alignment D D C D C unevenness Image- D D
C D C sticking
TABLE-US-00096 TABLE 96 Comparative Comparative Comparative Example
46 Example 47 Example 48 Liquid crystal Comparative Comparative
Comparative composition Liquid Crystal Liquid Crystal Liquid
Crystal Composition 6 Composition 6 Composition 6 Sealant Sealant
(6) Sealant (7) Sealant (8) VHR 97.5 97.8 97.3 Alignment C C C
unevenness Image-sticking D C D
[0388] The liquid crystal display devices of Comparative Examples
25 to 48 had lower VHRs than those according to the present
invention and exhibited unacceptable alignment unevenness and
image-sticking.
Comparative Examples 49 to 72
[0389] VA liquid crystal display devices of Comparative Examples 49
to 72 were fabricated as in Comparative Example 1 except that
Comparative Liquid Crystal Composition 1 was replaced with
Comparative Liquid Crystal Compositions 7 to 9 shown in the
following tables. The resulting liquid crystal display devices were
tested for VHR and were evaluated for alignment unevenness and
image-sticking. The results are shown in the following tables.
TABLE-US-00097 TABLE 97 Comparative Comparative Comparative Liquid
Crystal Liquid Crystal Liquid Crystal Composition 7 Composition 8
Composition 9 3-Cy-Cy-2 28% 3-Cy-Cy-2 25% 3-Cy-Cy-2 28% 3-Cy-Cy-4
10% 3-Cy-Cy-4 9% 3-Cy-Cy-4 8% 3-Cy-Ph-O1 7% 3-Cy-Ph-O1 6%
3-Cy-Ph-O1 7% 2-Cy-Ph5-O2 2% 2-Cy-Ph5-O2 2% 2-Cy-Ph5- 2% O2
3-Cy-Ph5-O4 2% 3-Cy-Ph5-O4 2% 3-Cy-Ph5- 2% O4 2-Cy-Ph-Ph5-O2 5%
2-Cy-Ph-Ph5-O2 5% 2-Cy-Ph- 5% Ph5-O2 3-Cy-Ph-Ph5-O2 5%
3-Cy-Ph-Ph5-O2 5% 3-Cy-Ph- 5% Ph5-O2 3-Cy-Cy-Ph5-O3 5%
3-Cy-Cy-Ph5-O3 5% 3-Cy-Cy- 5% Ph5-O3 4-Cy-Cy-Ph5-O2 5%
4-Cy-Cy-Ph5-O2 5% 4-Cy-Cy- 5% Ph5-O2 5-Cy-Cy-Ph5-O2 5%
5-Cy-Cy-Ph5-O2 5% 5-Cy-Cy- 5% Ph5-O2 3-Ph-Ph5-Ph-2 2% 3-Ph-Ph5-Ph-2
2% 3-Ph-Ph5- 2% Ph-2 4-Ph-Ph5-Ph-2 2% 4-Ph-Ph5-Ph-2 2% 4-Ph-Ph5- 2%
Ph-2 5-Ph-Ph-1 22% 5-Ph-Ph-1 19% 5-Ph-Ph-1 15% 3-Cy-Cy-Ph-1 8%
3-Cy-Cy- 9% Ph-1
TABLE-US-00098 TABLE 98 Comparative Comparative Comparative
Comparative Comparative Example 49 Example 50 Example 51 Example 52
Example 53 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 7
Composition 7 Composition 7 Composition 7 Composition 7 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.0 97.1 97.7 97.0 97.5 Alignment D D C C C unevenness Image- D D
C D C sticking
TABLE-US-00099 TABLE 99 Comparative Comparative Comparative Example
54 Example 55 Example 56 Liquid crystal Comparative Comparative
Comparative composition Liquid Crystal Liquid Crystal Liquid
Crystal Composition 7 Composition 7 Composition 7 Sealant Sealant
(6) Sealant (7) Sealant (8) VHR 97.4 97.8 97.2 Alignment D C C
unevenness Image-sticking D C D
TABLE-US-00100 TABLE 100 Comparative Comparative Comparative
Comparative Comparative Example 57 Example 58 Example 59 Example 60
Example 61 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 8
Composition 8 Composition 8 Composition 8 Composition 8 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.2 97.4 98.0 97.3 97.7 Alignment D D C D C unevenness Image- D D
C D D sticking
TABLE-US-00101 TABLE 101 Comparative Comparative Comparative
Example 62 Example 63 Example 64 Liquid crystal Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Composition 8 Composition 8 Composition 8 Sealant
Sealant (6) Sealant (7) Sealant (8) VHR 97.7 97.9 97.5 Alignment D
C D unevenness Image-sticking C D C
TABLE-US-00102 TABLE 102 Comparative Comparative Comparative
Comparative Comparative Example 65 Example 66 Example 67 Example 68
Example 69 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 9
Composition 9 Composition 9 Composition 9 Composition 9 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.3 97.4 98.1 97.4 97.8 Alignment D D C D C unevenness Image- D D
C D C sticking
TABLE-US-00103 TABLE 103 Comparative Comparative Comparative
Example 70 Example 71 Example 72 Liquid crystal Cornparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Composition 9 Composition 9 Composition 9 Sealant
Sealant (6) Sealant (7) Sealant (8) VHR 97.6 97.9 97.5 Alignment C
C C unevenness Image-sticking D D D
[0390] The liquid crystal display devices of Comparative Examples
49 to 72 had lower VHRs than those according to the present
invention and exhibited unacceptable alignment unevenness and
image-sticking.
Comparative Examples 73 to 88
[0391] VA liquid crystal display devices of Comparative Examples 73
to 88 were fabricated as in Comparative Example 1 except that
Comparative Liquid Crystal Composition 1 was replaced with
Comparative Liquid Crystal Compositions 10 and 11 shown in the
following tables. The resulting liquid crystal display devices were
tested for VHR and were evaluated for alignment unevenness and
image-sticking. The results are shown in the following tables.
TABLE-US-00104 TABLE 104 Comparative Liquid Crystal Comparative
Liquid Crystal Composition 10 Composition 11 3-Cy-Cy-2 10%
3-Cy-Cy-4 11% 3-Cy-Cy-4 3% 3-Cy-Cy-5 5% 3-Cy-Cy-5 2% 2-Cy-Ph5-O2
16% 3-Cy-Ph-O1 2% 3-Cy-Ph5-O4 16% 2-Cy-Ph5-O2 16% 2-Cy-Ph-Ph5-O2
12% 3-Cy-Ph5-O4 16% 3-Cy-Ph-Ph5-O2 12% 2-Cy-Ph-Ph5-O2 12%
3-Cy-Cy-Ph5-O3 9% 3-Cy-Ph-Ph5-O2 11% 4-Cy-Cy-Ph5-O2 9%
3-Cy-Cy-Ph5-O3 9% 5-Cy-Cy-Ph5-O2 8% 4-Cy-Cy-Ph5-O2 9% 3-Cy-Cy-Ph-1
2% 5-Cy-Cy-Ph5-O2 9% 3-Cy-Cy-Ph-1 1%
TABLE-US-00105 TABLE 105 Comparative Comparative Comparative
Comparative Comparative Example 73 Example 74 Example 75 Example 76
Example 77 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 10
Composition 10 Composition Composition Composition 10 10 10 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.2 97.3 98.0 97.3 97.8 Alignment C D C D C unevenness Image- D D
C D C sticking
TABLE-US-00106 TABLE 106 Comparative Comparative Comparative
Example 78 Example 79 Example 80 Liquid crystal Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Composition 10 Composition 10 Composition 10 Sealant
Sealant (6) Sealant (7) Sealant (8) VHR 97.6 97.7 97.5 Alignment D
C D unevenness Image-sticking C C C
TABLE-US-00107 TABLE 107 Comparative Comparative Comparative
Comparative Comparative Example 81 Example 82 Example 83 Example 84
Example 85 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 11
Composition 11 Composition Composition Composition 11 11 11 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.0 97.2 97.9 97.1 97.6 Alignment D D C D C unevenness Image- D D
C C C sticking
TABLE-US-00108 TABLE 108 Comparative Comparative Comparative
Example 86 Example 87 Example 88 Liquid crystal Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Composition 11 Composition 11 Composition 11 Sealant
Sealant (6) Sealant (7) Sealant (8) VHR 97.5 97.7 97.4 Alignment C
C C unevenness Image-sticking D D D
[0392] The liquid crystal display devices of Comparative Examples
73 to 88 had lower VHRs than those according to the present
invention and exhibited unacceptable alignment unevenness and
image-sticking.
Comparative Examples 89 to 112
[0393] VA liquid crystal display devices of Comparative Examples 89
to 112 were fabricated as in Comparative Example 1 except that
Comparative Liquid Crystal Composition 1 was replaced with
Comparative Liquid Crystal Compositions 12 to 14 shown in the
following tables. The resulting liquid crystal display devices were
tested for VHR and were evaluated for alignment unevenness and
image-sticking. The results are shown in the following tables.
TABLE-US-00109 TABLE 109 Comparative Comparative Comparative Liquid
Crystal Liquid Crystal Liquid Crystal Composition 12 Composition 13
Composition 14 3-Cy-Cy-2 25% 3-Cy-Cy-2 27% 3-Cy-Cy-2 30% 3-Cy-Cy-4
12% 3-Cy-Cy-4 12% 3-Cy-Cy-4 12% 3-Cy-Cy-5 7% 3-Cy-Cy-5 6% 3-Cy-Cy-5
9% 3-Cy-Ph-O1 11% 3-Cy-Ph-O1 9% 2-Cy-Ph5-O2 4% 2-Cy-Ph5-O2 5%
2-Cy-Ph5-O2 5% 3-Cy-Ph5-O4 4% 3-Cy-Ph5-O4 5% 3-Cy-Ph5-O4 5%
2-Cy-Ph-Ph5-O2 5% 2-Cy-Ph- 4% 2-Cy-Ph- 4% 3-Cy-Ph-Ph5-O2 5% Ph5-O2
Ph5-O2 3-Cy-Ph- 4% 3-Cy-Ph- 3% 3-Cy-Cy-Ph5-O3 3% Ph5-O2 Ph5-O2
3-Cy-Cy- 2% 3-Cy-Cy- 3% 4-Cy-Cy-Ph5-O2 3% Ph5-O3 Ph5-O3 4-Cy-Cy- 2%
4-Cy-Cy- 2% 5-Cy-Cy-Ph5-O2 3% Ph5-O2 Ph5-O2 5-Cy-Cy- 2% 5-Cy-Cy- 2%
3-Ph-Ph5-Ph-2 3% Ph5-O2 Ph5-O2 3-Ph-Ph5-Ph-2 5% 3-Ph-Ph5-Ph-2 6%
4-Ph-Ph5-Ph-2 3% 4-Ph-Ph5-Ph-2 5% 4-Ph-Ph5-Ph-2 4% 3-Cy-Cy-Ph-1 16%
3-Cy-Cy-Ph-1 11% 3-Cy-Cy-Ph-1 12%
TABLE-US-00110 TABLE 110 Comparative Comparative Comparative
Comparative Comparative Example 89 Example 90 Example 91 Example 92
Example 93 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 12
Composition 12 Composition Composition Composition 12 12 12 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
96.9 97.1 97.8 97.0 97.5 Alignment D C C D D unevenness Image- D D
C D C sticking
TABLE-US-00111 TABLE 111 Comparative Comparative Comparative
Example 94 Example 95 Example 96 Liquid crystal Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Composition 12 Composition 12 Composition 12 Sealant
Sealant (6) Sealant (7) Sealant (8) VHR 97.3 97.6 97.3 Alignment C
C D unevenness Image-sticking C C C
TABLE-US-00112 TABLE 112 Comparative Comparative Comparative
Comparative Comparative Example 97 Example 98 Example 99 Example
100 Example 101 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 13
Composition 13 Composition Composition Composition 13 13 13 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.2 97.3 97.9 97.2 97.7 Alignment D D D C D unevenness Image- D D
C D C sticking
TABLE-US-00113 TABLE 113 Comparative Comparative Comparative
Example 102 Example 103 Example 104 Liquid crystal Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Composition 13 Composition 13 Composition 13 Sealant
Sealant (6) Sealant (7) Sealant (8) VHR 97.6 97.9 97.4 Alignment C
C C unevenness Image-sticking C C C
TABLE-US-00114 TABLE 114 Comparative Comparative Comparative
Comparative Comparative Example 105 Example 106 Example 107 Example
108 Example 109 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 14
Composition 14 Composition Composition Composition 14 14 14 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.0 97.2 98.0 97.1 97.7 Alignment D C C D C unevenness Image- D D
C D D sticking
TABLE-US-00115 TABLE 115 Comparative Comparative Comparative
Example 110 Example 111 Example 112 Liquid crystal Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Composition 14 Composition 14 Composition 14 Sealant
Sealant (6) Sealant (7) Sealant (8) VHR 97.7 97.9 97.4 Alignment C
C D unevenness Image-sticking D C D
[0394] The liquid crystal display devices of Comparative Examples
89 to 112 had lower VHRs than those according to the present
invention and exhibited unacceptable alignment unevenness and
image-sticking.
Comparative Examples 113 to 120
[0395] VA liquid crystal display devices of Comparative Examples
113 to 120 were fabricated as in Comparative Example 1 except that
Comparative Liquid Crystal Composition 1 was replaced with
Comparative Liquid Crystal Composition 15 shown in the following
table. The resulting liquid crystal display devices were tested for
VHR and were evaluated for alignment unevenness and image-sticking.
The results are shown in the following tables.
TABLE-US-00116 TABLE 116 Comparative Liquid Crystal Composition 15
3-Cy-Cy-2 14% 3-Cy-Ph-O1 4% 2-Cy-Ph5-O2 3% 2-Cy-Ph-Ph5-O2 13%
3-Cy-Ph-Ph5-O2 13% 3-Cy-Cy-Ph5-O3 12% 4-Cy-Cy-Ph5-O2 12%
5-Cy-Cy-Ph5-O2 12% 3-Ph-Ph5-Ph-2 8% 4-Ph-Ph5-Ph-2 8% 5-Ph-Ph-1
1%
TABLE-US-00117 TABLE 117 Comparative Comparative Comparative
Comparative Comparative Example 113 Example 114 Example 115 Example
116 Example 117 Liquid crystal Comparative Comparative Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Liquid Crystal Liquid Crystal Composition 15
Composition 15 Composition Composition Composition 15 15 15 Sealant
Sealant (1) Sealant (2) Sealant (3) Sealant (4) Sealant (5) VHR
97.3 97.4 97.9 97.3 97.7 Alignment D C C D C unevenness Image- D D
D D C sticking
TABLE-US-00118 TABLE 118 Comparative Comparative Comparative
Example 118 Example 119 Example 120 Liquid crystal Comparative
Comparative Comparative composition Liquid Crystal Liquid Crystal
Liquid Crystal Composition 15 Composition 15 Composition 15 Sealant
Sealant (6) Sealant (7) Sealant (8) VHR 97.5 97.7 97.6 Alignment D
C D unevenness Image-sticking C C D
[0396] The liquid crystal display devices of Comparative Examples
113 to 120 had lower VHRs than those according to the present
invention and exhibited unacceptable alignment unevenness and
image-sticking.
Comparative Examples 121 to 136
[0397] Liquid crystal display devices of Comparative Examples 121
to 136 were fabricated as in Examples 1, 6, 36, 61, 66, 91, 96, and
126 except that the sealant was replaced with Comparative Sealants
(C1) and (C2). The resulting liquid crystal display devices were
tested for VHR and were evaluated for alignment unevenness and
image-sticking. The results are shown in the following tables.
TABLE-US-00119 TABLE 119 Comparative Comparative Comparative
Comparative Example 121 Example 122 Example 123 Example 124 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal Liquid Crystal
composition Composition 1 Composition 2 Composition 8 Composition
13 Sealant Comparative Comparative Comparative Comparative Sealant
(C1) Sealant (C1) Sealant (C1) Sealant (C1) VHR 98.0 97.9 97.5 97.5
Alignment C C D D unevenness Image-sticking D D D D
TABLE-US-00120 TABLE 120 Comparative Comparative Comparative
Comparative Example 125 Example 126 Example 127 Example 128 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal Liquid Crystal
composition Composition 14 Composition 19 Composition 20
Composition 26 Sealant Comparative Comparative Comparative
Comparative Sealant (C1) Sealant (C1) Sealant (C1) Sealant (C1) VHR
97.6 97.7 97.6 97.4 Alignment D D D D unevenness Image-sticking D D
D D
TABLE-US-00121 TABLE 121 Comparative Comparative Comparative
Comparative Example 129 Example 130 Example 131 Example 132 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal Liquid Crystal
composition Composition 1 Composition 2 Composition 8 Composition
13 Sealant Comparative Comparative Comparative Comparative Sealant
(C2) Sealant (C2) Sealant (C2) Sealant (C2) VHR 97.5 97.6 97.2 97.3
Alignment D C D D unevenness Image-sticking D D D D
TABLE-US-00122 TABLE 122 Comparative Comparative Comparative
Comparative Example 133 Example 134 Example 135 Example 136 Liquid
crystal Liquid Crystal Liquid Crystal Liquid Crystal Liquid Crystal
composition Composition 14 Composition 19 Composition 20
Composition 26 Sealant Comparative Comparative Comparative
Comparative Sealant (C2) Sealant (C2) Sealant (C2) Sealant (C2) VHR
97.4 97.4 97.4 97.2 Alignment D D D D unevenness Image-sticking D D
D D
[0398] The liquid crystal display devices of Comparative Examples
121 to 136 had lower VHRs than those according to the present
invention and exhibited unacceptable alignment unevenness and
image-sticking.
* * * * *